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Factors that have an effect on degradation of diclofenac in aqueous solution by gamma ray irradiation

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Abstract

Purpose

Gamma ray irradiation is considered as an effective way to degrade diclofenac. However, due to the extensive coexisting substances in natural waters, the use of gamma ray irradiation for degradation is often influenced by multiple factors. The various factors that affect degradation efficiency, such as initial diclofenac concentration, initial pH, and the concentration of the additives including H2O2 (·OH radical promoter), CH3OH (·OH radical scavenger), thiourea (·OH, H·, and e aq scavenger), humic acid, and NO 3 (coexisting substances in natural waters), are investigated. Furthermore, possible intermediate products are identified and corresponding transformation pathways are proposed.

Methods

Degradation experiments were performed in a 50-mL airtight Pyrex bottle loaded with 25 mL of diclofenac solutions at various initial concentrations of 20.5, 30.4, and 50.1 mg L−1. The radiation doses were controlled at 0, 0.3, 0.5, 0.7, and 1.0 kGy.

Results

Study results indicate that: (1) The degradation efficiency of diclofenac decreases with the increase of its initial concentration. (2) The degradation efficiency is higher under acidic conditions than in neutral and alkaline media. (3) The results obtained when H2O2, CH3OH, and thiourea were added show that the degradation of diclofenac takes place via two pathways: oxidation by ·OH radicals and reduction by e aq and H·. (4) The extensive coexisting substances in natural waters, such as humic acid and NO 3 , do not affect the degradation efficiency. Based on the identified intermediates, it is proposed that transformation pathways are initiated mainly by H·, e aq , and ·OH.

Conclusion

Gamma ray irradiation effectively degrades diclofenac.

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References

  • Benotti MJ, Trenholm RA, Vanderford BJ, Standford BD, Snyder SA (2009) Pharmaceuticals and endocrine disrupting compounds in US drinking water. Environ Sci Technol 43(3):597–603

    Article  CAS  Google Scholar 

  • Brezonik PL, Fulkerson-Brekken J (1998) Nitrate-induced photolysis in natural waters: controls on concentrations of hydroxyl radical photo-intermediates by natural scavenging agents. Environ Sci Technol 32:3004–3010

    Article  CAS  Google Scholar 

  • Buser HR, Poiger T, Müller M (1999) Occurrence and environmental behavior of the chiral pharmaceutical drug ibuprofen in surface waters and in wastewater. Environ Sci Technol 33:2529–2535

    Article  CAS  Google Scholar 

  • Choi JI, Kim JK, Kim JH, Kweon DK, Lee JW (2010) Degradation of hyaluronic acid powder by electron beam irradiation, gamma ray irradiation, microwave irradiation and thermal treatment: a comparative study. Carbohydr Polym 79(4):1080–1085

    Article  CAS  Google Scholar 

  • Cleuvers M (2004) Mixture toxicity of the anti-inflammatory drugs diclofenac, ibuprofen, naproxen, and acetylsalicylic acid. Ecotoxicol Environ Saf 59:309–315

    Article  CAS  Google Scholar 

  • Flox C, Ammar S, Arias C, Brillas E, Vargas-Zavala AV, Abdelhedi R (2006) Electro-Fenton and photoelectro-Fenton degradation of indigo carmine in acidic aqueous medium. Appl Catal B Environ 67(1–2):93–104

    Article  CAS  Google Scholar 

  • Güyer GT, Ince NH (2011) Degradation of diclofenac in water by homogeneous and heterogeneous sonolysis. Ultrason Sonochem 18:114–119

    Article  Google Scholar 

  • Hartmann J, Bartels P, Mau U, Witter M, Tümpling WV, Hofmann J, Nietzschmann E (2008) Degradation of the drug diclofenac in water by sonolysis in presence of catalysts. Chemosphere 70:453–461

    Article  CAS  Google Scholar 

  • Huber M, Canonica S, Park GY, von Gunten U (2003) Oxidation of pharmaceuticals during ozonation and advanced oxidation processes. Environ Sci Technol 37:1016–1024

    Article  CAS  Google Scholar 

  • Irmak S, Yavuz HI, Erbatur O (2006) Degradation of 4-chloro-2-methylphenol in aqueous solution by electro-Fenton and photoelectro-Fenton processes. Appl Catal B Environ 63:243–248

    Article  CAS  Google Scholar 

  • Ito R, Miura N, Ushiro M, Kawaguchi M, Nakamura H, Iguchi H, Ogino JI, Oishi M, Wakui N, Iwasaki Y, Saito K, Nakazawa H (2009) Effect of gamma-ray irradiation on degradation of di(2-ethylhexyl) phthalate in polyvinyl chloride sheet. Int J Pharm 376(1–2):213–218

    Article  CAS  Google Scholar 

  • Joss A, Zabczynski S, Göbel A, Hoffmann B, Löffler D, McArdell CS, Ternes TA, Thomsen A, Siegrist H (2006) Biological degradation of pharmaceuticals in municipal wastewater treatment: proposing a classification scheme. Water Res 40(8):1686–1696

    Article  CAS  Google Scholar 

  • Junko K (1997) Enhancement of wastewater and sludge treatment by ionizing radiation. In: Proceeding of a workshop on the potential for engineering scale processing of waste treatment streams by electron-beam irradiation, University of Miami, Coral Gables, pp. 30–172

  • Kim SD, Cho J, Kim IS, Vanderford BJ, Snyder SA (2007) Occurrence and removal of pharmaceuticals and endocrine disruptors in South Korean surface, drinking, and waste waters. Water Res 41(5):1013–1021

    Article  CAS  Google Scholar 

  • Kimura A, Taguchi M, Ohtani Y, Takigami M, Shimada Y, Kojima T, Hiratsuka H, Namba H (2006) Decomposition of p-nonylphenols in water and elimination of their estrogen activities by 60Co γ-ray irradiation. Radiat Phys Chem 75(1):61–69. doi:10.1016/j.radphyschem.2005.05.016

    Article  CAS  Google Scholar 

  • Kosjek T, Žigon D, Kralj B, Heath E (2008) The use of quadrupole-time-of-flight mass spectrometer for the elucidation of diclofenac biotransformation products in wastewater. J Chromatogr A 1215(1–2):57–63

    Article  CAS  Google Scholar 

  • Leónidas AP, Sixto M, Wolfgang G, Ana A, Thurman EM, Imma F, Amadeo RF (2005) Photo-Fenton degradation of diclofenac: identification of main intermediates and degradation pathway. Environ Sci Technol 39:8300–8306

    Article  Google Scholar 

  • Lishman L, Smyth SA, Sarafin K, Kleywegt S, Toito J, Peart T, Lee B, Servos M, Beland M, Seto P (2006) Occurrence and reductions of pharmaceuticals and personal care products and estrogens by municipal wastewater treatment plants in Ontario, Canada. Sci Total Environ 367:544–558

    Article  CAS  Google Scholar 

  • Loraine GA, Pettigrove ME (2006) Seasonal variations in concentrations of pharmaceuticals and personal care products in drinking water and reclaimed wastewater in southern California. Environ Sci Technol 40:687–695

    Article  CAS  Google Scholar 

  • Madhavan J, Kumar PSS, Anandan S, Zhou MF, Grieser F, Ashokkumar M (2010) Ultrasound assisted photocatalytic degradation of diclofenac in an aqueous environment. Chemosphere 80:747–752

    Article  CAS  Google Scholar 

  • Mcclellan K, Halden RU (2010) Pharmaceuticals and personal care products in archived US biosolids from the 2001 EPA national sewage sludge survey. Water Res 44(2):658–668

    Article  CAS  Google Scholar 

  • Monteiro SC, Boxall ABA (2010) Occurrence and fate of human pharmaceuticals in the environment. Rev Environ Contam Toxicol 202:53–154

    Article  CAS  Google Scholar 

  • Nickelsen MG, Cooper WJ, Lin KJ, Kurucz CN, Waite TD (1994) High-energy electron-beam generation of oxidants for the treatment of benzene and toluene in the presence of radical scavengers. Water Res 28(5):1227–1237

    Article  CAS  Google Scholar 

  • Pérez-Estrada LA, Maldonado MI, Gernjak W, Agüera A, Fernández-Alba AR, Ballesteros MM, Malato S (2005) Decomposition of diclofenac by solar driven photocatalysis at pilot plant scale. Catal Today 101:219–226. doi:10.1016/j.cattod.2005.03.013

    Article  Google Scholar 

  • Poiger T, Buser HR, Müller MD (2001) Photodegradation of the pharmaceutical drug diclofenac in a lake: pathway, field measurements, and mathematical modeling. Environ Toxicol Chem 20:256–263

    Article  CAS  Google Scholar 

  • Radjenović J, Petrović M, Barceló D (2009) Fate and distribution of pharmaceuticals in wastewater and sewage sludge of the conventional activated sludge (CAS) and advanced membrane bioreactor (MBR) treatment. Water Res 43:831–841

    Article  Google Scholar 

  • Ravina M, Campanella L, Kiwi J (2002) Accelerated mineralization of the drug Diclofenac via Fenton reactions in a concentric photo-reactor. Water Res 36:3553–3560

    Article  CAS  Google Scholar 

  • Rosal R, Rodriguez A, Perdigon-Melon JA, Petre A, Garcia-Calvo E, Gomez MJ, Aguera A, Fernandez-Alba AR (2010) Occurrence of emerging pollutants in urban wastewater and their removal through biological treatment followed by ozonation. Water Res 44:578–588

    Article  CAS  Google Scholar 

  • Sandvik SLH, Bilski P, Pakulski JD, Chignell CF, Coffin RB (2000) Photogeneration of singlet oxygen and free radicals in dissolved organic matter isolated from the Mississippi and Atchafalaya river plumes. Mar Chem 69:139–152

    Article  CAS  Google Scholar 

  • Singh A, Kremers W (2002) Radiolytic dechlorination of polychlorinated biphenyls using alkaline 2-propanol solutions. Radiat Phys Chem 65:467–472

    Article  CAS  Google Scholar 

  • Strukul G (ed) (1992) Catalytic oxidations with hydrogen peroxide as oxidant. Kluwer Academic, Boston

    Google Scholar 

  • Stülten D, Zuhlke S, Lamshoft M, Spiteller M (2008) Occurrence of diclofenac and selected metabolites in sewage effluents. Sci Total Environ 405:310–316

    Article  Google Scholar 

  • Vincenzo N, Vincenzo B, Daniele R, Despo K (2009) Degradation of diclofenac during sonolysis, ozonation and their simultaneous application. Ultrason Sonochem 16:790–794

    Article  Google Scholar 

  • Vogna D, Marotta R, Napolitano A, Andreozzi R, d'Ischia M (2004) Advanced oxidation of the pharmaceutical drug diclofenac with UV/H2O2 and ozone. Water Res 38:414–422

    Article  CAS  Google Scholar 

  • Weigel S, Kallenborn R, Hühnerfuss H (2004) Simultaneous solid-phase extraction of acidic, neutral and basic pharmaceuticals from aqueous samples at ambient (neutral) pH and their determination by gas chromatography-mass spectrometry. J Chromatogr A 1023:183–195

    Article  CAS  Google Scholar 

  • Yamazaki M, Sawai T, Sawai T, Yamazaki K, Kawaguchi S (1983) Combined gamma-ray irradiation activated-sludge treatment of humic-acid solution from landfill leachate. Water Res 17(12):1811–1814

    Article  CAS  Google Scholar 

  • Zhan MJ, Yang X, Xian QM, Kong LG (2006) Photosensitized degradation of bisphenol A involving reactive oxygen species in the presence of humic substances. Chemosphere 63:378–386

    Article  CAS  Google Scholar 

  • Zhang JB, Zheng Z, Zhao T, Zhao YF, Wang LH, Zhong Y, Xu Y (2008a) Radiation-induced reduction of diuron by gamma-ray irradiation. J Hazard Mater 151(2–3):465–472

    Article  CAS  Google Scholar 

  • Zhang YJ, Geissen SU, Gal C (2008b) Carbamazepine and diclofenac: removal in wastewater treatment plants and occurrence in water bodies. Chemosphere 73:1151–1161

    Article  CAS  Google Scholar 

Download references

Acknowledgments

Zheng Zheng gratefully acknowledges support from the Natural Science Foundation of China (Foundation item No. 10475040). We would like to thank Zhao YongFu for his help in the experimental work.

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Correspondence to Zheng Zheng.

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Responsible editor: Philippe Garrigues

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Liu, Q., Luo, X., Zheng, Z. et al. Factors that have an effect on degradation of diclofenac in aqueous solution by gamma ray irradiation. Environ Sci Pollut Res 18, 1243–1252 (2011). https://doi.org/10.1007/s11356-011-0457-9

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  • DOI: https://doi.org/10.1007/s11356-011-0457-9

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