Advertisement

Environmental Science and Pollution Research

, Volume 25, Issue 28, pp 27783–27795 | Cite as

Mineralization of humic acids (HAs) by a solar photo-Fenton reaction mediated by ferrioxalate complexes: commercial HAs vs extracted from leachates

  • Ana P. F. Santos
  • Bianca M. Souza
  • Tânia F. C. V. SilvaEmail author
  • Rodrigo P. Cavalcante
  • Silvio C. Oliveira
  • Amílcar MachulekJr.
  • Rui A. R. Boaventura
  • Vítor J. P. VilarEmail author
New Challenges in the Application of Advanced Oxidation Processes

Abstract

The mineralization of bio-recalcitrant humic acids (HAs) by a solar photo-Fenton (SPF) process was investigated in aqueous system, in order to understand its abatement in real high-HA content matrices, such as sanitary landfill leachates. SPF reactions were performed in tubular photoreactors with CPCs at lab-scale (simulated solar light) and pilot-scale (natural sunlight). Considering the experimental conditions selected for this work, the formation of insoluble HA-Fe3+ complexes was observed. Thus, to avoid HA precipitation, oxalic acid (Ox) was added, since Fe3+-Ox complexes present a higher stability constant. The effect of different process variables on the performance of SPF reaction mediated by ferrioxalate complexes (SPFF) was assessed with excess of H2O2 (50–250 mg L−1), at lab-scale: (i) pH (2.8–4.0); (ii) initial iron concentration (20–60 mg Fe3+ L−1); (iii) iron-oxalate molar ratio (Fe3+-Ox of 1:3 and 1:6); (iv) temperature (20–40 °C); (v) UV irradiance (21–58 WUV m−2); and (vi) commercial-HA concentration (50–200 mg C L−1). At the best lab conditions (40 mg Fe3+ L−1, pH 2.8, 30 °C, 1.6 Fe3+-Ox molar ratio, 41 WUV m−2), commercial HAs’ mineralization profile was also compared with HAs extracted from a sanitary landfill leachate, achieving 88 and 91% of dissolved organic carbon removal, respectively, after 3-h irradiation (8.7 kJUV L−1). Both reactions followed the same trend, although a 2.1-fold increase in the reaction rate was observed for the leachate-HA experiment, due to its lower humification degree. At pilot-scale, under natural sunlight, 95% HA mineralization was obtained, consuming 42 mM of H2O2 and 5.9 kJUV L−1 of accumulated UV energy. However, a pre-oxidation during 2.8 kJUV L−1 (12 mM H2O2) was enough to obtain a biodegradability index of 89%, showing the strong feasibility to couple the SPFF process to a downstream biological oxidation, with low chemicals and energetic demands.

Graphical abstract

Keywords

Landfill leachates Solar-driven photo-Fenton Ferrioxalate complexes Biodegradability 

Notes

Funding information

This work was financially supported by project “AIProcMat@N2020 - Advanced Industrial Processes and Materials for a Sustainable Northern Region of Portugal 2020”, with reference NORTE-01-0145-FEDER-000006, supported by Norte Portugal Regional Operational Programme (NORTE 2020), under Portugal 2020 Partnership Agreement, through European Regional Development Fund (ERDF), and of Project POCI-01-0145-FEDER-006984—Associate Laboratory LSRE-LCM funded by ERDF through COMPETE 2020—Programa Operacional Competitividade e Internacionalização (POCI)—and by national funds through FCT—Fundação para a Ciência e a Tecnologia. Ana Santos acknowledges her Ph.D. fellowship (BEX 10029/13-3 process) supported by CAPES and CNPq. Bianca Souza acknowledges her Ph.D. scholarship by program Brazil/Portugal CAPES/FCT 308/11. Tânia Silva acknowledges her Ph.D. scholarship, reference SFRH/BD/73510/2010, supported by FCT. V.J.P. Vilar acknowledges the FCT Investigator 2013 Programme (IF/00273/2013).

Supplementary material

11356_2018_1561_MOESM1_ESM.doc (1.1 mb)
ESM 1 (DOC 1161 kb)

References

  1. Aguer JP, Richard C (1996) Reactive species produced on irradiation at 365 nm of aqueous solutions of humic acids. J Photochem Photobiol A Chem 93:193–198CrossRefGoogle Scholar
  2. Babuponnusami A, Muthukumar K (2014) A review on Fenton and improvements to the Fenton process for wastewater treatment. J Environ Chem Eng 2:557–572CrossRefGoogle Scholar
  3. Bautitz IR, Nogueira RFP (2007) Degradation of tetracycline by photo-Fenton process—solar irradiation and matrix effects. J Photochem Photobiol A Chem 187:33–39CrossRefGoogle Scholar
  4. Boye B, Dieng MM, Brillas E (2002) Degradation of herbicide 4-chlorophenoxyacetic acid by advanced electrochemical oxidation methods. Environ Sci Technol 36:3030–3035CrossRefGoogle Scholar
  5. Braun AM, Frimmel FH, Hoigné J (1986) Singlet oxygen analysis in irradiated surface waters. Int J Environ Anal Chem 27:137–149CrossRefGoogle Scholar
  6. Brigante M, Zanini G, Avena M (2009) Effect of pH, anions and cations on the dissolution kinetics of humic acid particles. Colloids Surf A Physicochem Eng Asp 347:180–186CrossRefGoogle Scholar
  7. Cavalcante RP, Dantas RF, Wender H, Bayarri B, González O, Giménez J, Esplugas S, Machulek A (2015) Photocatalytic treatment of metoprolol with B-doped TiO2: effect of water matrix, toxicological evaluation and identification of intermediates. Appl Catal B Environ 176-177:173–182CrossRefGoogle Scholar
  8. Cavalcante RP, Dantas RF, Bayarri B, González O, Giménez J, Esplugas S, Machulek A (2016) Photocatalytic mechanism of metoprolol oxidation by photocatalysts TiO2 and TiO2 doped with 5% B: primary active species and intermediates. Appl Catal B Environ 194:111–122CrossRefGoogle Scholar
  9. Cheng WP (2002) Comparison of hydrolysis/coagulation behavior of polymeric and monomeric iron coagulants in humic acid solution. Chemosphere 47:963–969CrossRefGoogle Scholar
  10. Clesceri LS, Greenberg AE, Eaton AD (2005) Standard Methods for Examination of Water & Wastewater. American Public Health Association (APHA), American Water Works Association (AWWA) & Water Environment Federation (WEF), Washington, DCGoogle Scholar
  11. Cooper WJ, Zika RG, Petasne RG, Plane JMC (1988) Photochemical formation of hydrogen peroxide in natural waters exposed to sunlight. Environ Sci Technol 22:1156–1160CrossRefGoogle Scholar
  12. Farré MJ, Doménech X, Peral J (2007) Combined photo-Fenton and biological treatment for Diuron and Linuron removal from water containing humic acid. J Hazard Mater 147:167–174CrossRefGoogle Scholar
  13. Faust BC, Hoffmann MR (1986) Photoinduced reductive dissolution of α-iron oxide (α-Fe2O3) by bisulfite. Environ Sci Technol 20:943–948CrossRefGoogle Scholar
  14. Fukushima M, Tatsumi K, Morimoto K (2000) The fate of aniline after a photo-Fenton reaction in an aqueous system containing iron(III), humic acid, and hydrogen peroxide. Environ Sci Technol 34:2006–2013CrossRefGoogle Scholar
  15. Fukushima M, Tatsumi K, Nagao S (2001) Degradation characteristics of humic acid during photo-Fenton processes. Environ Sci Technol 35:3683–3690CrossRefGoogle Scholar
  16. Ghaggour E, Davies G (2001) Humic substances: structures, models and functions, 19. Royal Society of Chemistry, CambridgeGoogle Scholar
  17. Goodman BA, Cheshire MV (1987) Characterization of iron-fulvic acid complexes using Mossbauer and EPR spectroscopy. Sci Total Environ 62:229–240CrossRefGoogle Scholar
  18. Kang K-H, Shin HS, Park H (2002) Characterization of humic substances present in landfill leachates with different landfill ages and its implications. Water Res 36:4023–4032CrossRefGoogle Scholar
  19. Klamerth N, Malato S, Agüera A, Fernández-Alba A, Mailhot G (2012) Treatment of municipal wastewater treatment plant effluents with modified photo-fenton as a tertiary treatment for the degradation of micro pollutants and disinfection. Environ Sci Technol 46:2885–2892CrossRefGoogle Scholar
  20. Legrini O, Oliveros E, Braun AM (1993) Photochemical processes for water treatment. Chem Rev 93:671–698CrossRefGoogle Scholar
  21. Lipczynska-Kochany E, Kochany J (2008) Effect of humic substances on the Fenton treatment of wastewater at acidic and neutral pH. Chemosphere 73:745–750CrossRefGoogle Scholar
  22. Motta FL, Melo BAG, Santana MHA (2016) Deprotonation and protonation of humic acids as a strategy for the technological development of pH-responsive nanoparticles with fungicidal potential. N Biotechnol 33:773–780CrossRefGoogle Scholar
  23. Nogueira RFP, Oliveira MC, Paterlini WC (2005) Simple and fast spectrophotometric determination of H2O2 in photo-Fenton reactions using metavanadate. Talanta 66:86–91CrossRefGoogle Scholar
  24. Nogueira AA, Souza BM, Dezotti MWC, Boaventura RAR, Vilar VJP (2017) Ferrioxalate complexes as strategy to drive a photo-FENTON reaction at mild pH conditions: a case study on levofloxacin oxidation. J Photochem Photobiol A Chem 345:109–123CrossRefGoogle Scholar
  25. OECD (1992) OECD guideline for testing of chemicals—test no. 302B: inherent biodegradability: Zahn-Wellens/ EVPA test. Organization for Economic Cooperation and Development, Paris, p 8Google Scholar
  26. Pajares A, Bregliani M, Natera J, Criado S, Miskoski S, Escalada JP, García NA (2011) Mechanism of the photosensitizing action of a mixture humic acid–riboflavin in the degradation of water-contaminants. J Photochem Photobiol A Chem 219:84–89CrossRefGoogle Scholar
  27. Park S-J, Yoon T-I (2009) Effects of iron species and inert minerals on coagulation and direct filtration for humic acid removal. Desalination 239:146–158CrossRefGoogle Scholar
  28. Pereira JH, Reis AC, Nunes OC, Borges MT, Vilar VJ, Boaventura RA (2014) Assessment of solar driven TiO2-assisted photocatalysis efficiency on amoxicillin degradation. Environ Sci Pollut Res Int 21:1292–1303CrossRefGoogle Scholar
  29. Piccolo A, Nardi S, Concheri G (1996) Micelle-1ike conformation of humic substances as revealed by size exclusion chromatography. Chemosphere 33:595–602CrossRefGoogle Scholar
  30. Safarzadeh-Amiri A, Bolton JR, Cater SR (1997) Ferrioxalate-mediated photodegradation of organic pollutants in contaminated water. Water Res 31:787–798CrossRefGoogle Scholar
  31. Silva TFCV, Soares PA, Manenti DR, Fonseca A, Saraiva I, Boaventura RAR, Vilar VJP (2017) An innovative multistage treatment system for sanitary landfill leachate depuration: studies at pilot-scale. Sci Total Environ 576:99–117CrossRefGoogle Scholar
  32. Soares PA, Silva TF, Manenti DR, Souza SM, Boaventura RA, Vilar VJ (2014) Insights into real cotton-textile dyeing wastewater treatment using solar advanced oxidation processes. Environ Sci Pollut Res Int 21:932–945CrossRefGoogle Scholar
  33. Souza BM, Dezotti MWC, Boaventura RAR, Vilar VJP (2014) Intensification of a solar photo-Fenton reaction at near neutral pH with ferrioxalate complexes: a case study on diclofenac removal from aqueous solutions. Chem Eng J 256:448–457CrossRefGoogle Scholar
  34. Souza BM, Marinho BA, Moreira FC, Dezotti MWC, Boaventura RAR, Vilar VJP (2017) Photo-Fenton oxidation of 3-amino-5-methylisoxazole: a by-product from biological breakdown of some pharmaceutical compounds. Environ Sci Pollut Res Int 24:6195–6204CrossRefGoogle Scholar
  35. Steinberg CEW (2003) Ecology of humic substances in freshwaters: determinants from geochemistry to ecological niches. Springer Berlin, HeidelbergCrossRefGoogle Scholar
  36. ThanhThuy TT, Feng H, Cai Q (2013) Photocatalytic degradation of pentachlorophenol on ZnSe/TiO2 supported by photo-Fenton system. Chem Eng J 223:379–387CrossRefGoogle Scholar
  37. Thurman EM, Malcolm RL (1981) Preparative isolation of aquatic humic substances. Environ Sci Technol 15:463–466CrossRefGoogle Scholar
  38. Tipping E, Rey-Castro C, Bryan SE, Hamilton-Taylor J (2002) Al(III) and Fe(III) binding by humic substances in freshwaters, and implications for trace metal speciation. Geochim Cosmochim Acta 66:3211–3224CrossRefGoogle Scholar
  39. van Schaik JWJ, Persson I, Kleja DB, Gustafsson JP (2008) EXAFS study on the reactions between iron and fulvic acid in acid aqueous solutions. Environ Sci Technol 42:2367–2373CrossRefGoogle Scholar
  40. Voelker BM, Sulzberger B (1996) Effects of fulvic acid on Fe(II) oxidation by hydrogen peroxide. Environ Sci Technol 30:1106–1114CrossRefGoogle Scholar
  41. Weber T, Allard T, Tipping E, Benedetti MF (2006) Modeling iron binding to organic matter. Environ Sci Technol 40:7488–7493CrossRefGoogle Scholar
  42. Zuo Y, Hoigne J (1992) Formation of hydrogen peroxide and depletion of oxalic acid in atmospheric water by photolysis of iron(III)-oxalato complexes. Environ Sci Technol 26:1014–1022CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  • Ana P. F. Santos
    • 1
    • 2
  • Bianca M. Souza
    • 1
  • Tânia F. C. V. Silva
    • 1
    Email author
  • Rodrigo P. Cavalcante
    • 2
  • Silvio C. Oliveira
    • 2
  • Amílcar MachulekJr.
    • 2
  • Rui A. R. Boaventura
    • 1
  • Vítor J. P. Vilar
    • 1
    Email author
  1. 1.Laboratory of Separation and Reaction Engineering-Laboratory of Catalysis and Materials (LSRE-LCM), Departamento de Engenharia Química, Faculdade de EngenhariaUniversidade do PortoPortoPortugal
  2. 2.Instituto de QuímicaUniversidade Federal de Mato Grosso do SulCampo GrandeBrazil

Personalised recommendations