Degradation of naproxen in chlorination and UV/chlorine processes: kinetics and degradation products

  • Yongze Liu
  • Yuqing Tang
  • Yongxin Wu
  • Li FengEmail author
  • Liqiu Zhang
Appropriate Technologies to Combat Water Pollution


Naproxen (NAP) is a nonsteroidal anti-inflammatory drug which has been widely used and frequently detected in water environments. This study investigated the NAP degradation in the chlorination and UV/chlorine disinfection processes, which usually acted as the last barriers for water treatment. The results showed that both chlorination and UV/chlorine disinfection could remove NAP effectively. At various chlorine dosages (0.1~0.5 mM), the contributions of chlorination and reactive radicals to the degradation of NAP in the UV/chlorine process were calculated to be 50.5~56.9% and 43.1~49.5%, respectively. However, the reactive radicals dominated in NAP degradation in alkaline solutions, while chlorination dominated in acidic conditions. The HCO3 (10~50 mM) slightly inhibited, Cl (10~50 mM) gradually promoted, and HA (1~5 mg/L) significantly reduced NAP degradation by UV/chlorine process. The degradation intermediates and products were obtained via high-performance liquid chromatography with QE-MS/MS; NAP was degraded by demethylation, acetylation, and dicarboxylic acid pathways during the chlorination and UV/chlorination processes.


Naproxen Chlorination UV/chlorine disinfection Kinetics Degradation products 


Funding information

This work was supported by the National Nature Science Foundation of China (51578066 and 51608036) and the Fundamental Research Funds for the Central Universities (No. 2015ZCQ-HJ-02).


  1. Acero JL, Benitez FJ, Real FJ, Roldan G (2010) Kinetics of aqueous chlorination of some pharmaceuticals and their elimination from water matrices. Water Res 44:4158–4170CrossRefGoogle Scholar
  2. Alexander SJ (1975) Clinical experience with naproxen in rheumatoid arthritis. Arch Intern Med 135:1429–1435CrossRefGoogle Scholar
  3. Arany E, Szabó RK, Apáti L, Alapi T, Ilisz I, Mazellier P, Dombi A, Gajda-Schrantz K (2013) Degradation of naproxen by UV, VUV photolysis and their combination. J Hazard Mater 262:151–157CrossRefGoogle Scholar
  4. Bendz D, Paxéus NA, Ginn TR, Loge FJ (2005) Occurrence and fate of pharmaceutically active compounds in the environment, a case study: höje river in Sweden. J Hazard Mater 122:195–204CrossRefGoogle Scholar
  5. Boyd GR, Zhang S, Grimm DA (2005) Naproxen removal from water by chlorination and biofilm processes. Water Res 39:668–676CrossRefGoogle Scholar
  6. Cai MQ, Feng L, Jiang J, Qi F, Zhang LQ (2013) Reaction kinetics and transformation of antipyrine chlorination with free chlorine. Water Res 47:2830–2842CrossRefGoogle Scholar
  7. Cai MQ, Feng L, Zhang LQ (2017) Transformation of aminopyrine in the presence of free available chlorine: kinetics, products, and reaction pathways. Chemosphere 171:625–634CrossRefGoogle Scholar
  8. Chin CJM, Chen TY, Lee M, Chang CF, Liu YT, Kuo YT (2014) Effective anodic oxidation of naproxen by platinum nanoparticles coated fto glass. J Hazard Mater 277:110–119CrossRefGoogle Scholar
  9. Christen V, Hickmann S, Rechenberg B, Fent K (2010) Highly active human pharmaceuticals in aquatic systems: a concept for their identification based on their mode of action. Aquat Toxicol 96:167–181CrossRefGoogle Scholar
  10. Coria G, Sirés I, Brillas E, Nava JL (2016) Influence of the anode material on the degradation of naproxen by Fenton-based electrochemical processes. Chem Eng J 304:817–825CrossRefGoogle Scholar
  11. Deborde M, Von Gunten U (2008) Reactions of chlorine with inorganic and organic compounds during water treatment—kinetics and mechanisms: a critical review. Water Res 42:13–51CrossRefGoogle Scholar
  12. Deng J, Shao Y, Gao N, Xia S, Tan C, Zhou S, Hu X (2013) Degradation of the antiepileptic drug carbamazepine upon different UV-based advanced oxidation processes in water. Chem Eng J 222:150–158CrossRefGoogle Scholar
  13. Dong H, Qiang Z, Hu J, Qu J (2017) Degradation of chloramphenicol by UV/chlorine treatment: kinetics, mechanism and enhanced formation of halonitromethanes. Water Res 121:178–185CrossRefGoogle Scholar
  14. Fang J, Fu Y, Shang C (2014) The roles of reactive species in micropollutant degradation in the UV/free chlorine system. Environ Sci Technol 48:1859–1868CrossRefGoogle Scholar
  15. Fernández C, González-Doncel M, Pro J, Carbonell G, Tarazona JV (2010) Occurrence of pharmaceutically active compounds in surface waters of the henares-jarama-tajo river system (Madrid, Spain) and a potential risk characterization. Sci Total Environ 408:543–551CrossRefGoogle Scholar
  16. Guo ZB, Lin YL, Xu B, Huang H, Zhang TY, Tian FX, Gao NY (2016) Degradation of chlortoluron during uv irradiation and uv/chlorine processes and formation of disinfection by-products in sequential chlorination. Chem Eng J 283:412–419CrossRefGoogle Scholar
  17. Hijnen WA, Beerendonk EF, Medema GJ (2006) Inactivation credit of uv radiation for viruses, bacteria and protozoan (oo)cysts in water: a review. Water Res 40:3–22CrossRefGoogle Scholar
  18. Jia XH, Feng L, Liu YZ (2018) Degradation behaviors and genetic toxicity variations of pyrazolone pharmaceuticals during chlorine dioxide disinfection process[J]. Chem Eng J 345:156–164CrossRefGoogle Scholar
  19. Kosaka K, Nakai T, Hishida Y, Asami M, Ohkubo K, Akiba M (2016) Formation of 2,6-dichloro-1,4-benzoquinone from aromatic compounds after chlorination. Water Res 110:48–55CrossRefGoogle Scholar
  20. Luo Y, Guo W, Ngo HH, Nghiem LD, Hai FI, Zhang J, Liang S, Wang XC (2014) A review on the occurrence of micropollutants in the aquatic environment and their fate and removal during wastewater treatment. Sci Total Environ 473-474:619–641CrossRefGoogle Scholar
  21. Luo S, Gao L, Wei Z, Spinney R, Dionysiou DD, Hu WP, Chai L, Xiao R (2018) Kinetic and mechanistic aspects of hydroxyl radical–mediated degradation of naproxen and reaction intermediates. Water Res 137:233–241CrossRefGoogle Scholar
  22. Morris JC (1966) The acid ionization constant of hocl from 5 to 35°C. J Phys Chem 70:3798–3805CrossRefGoogle Scholar
  23. Rosal R, Rodríguez A, Perdigón-Melón JA, Petre A, García-Calvo E, Gómez MJ, Agüera A, Fernández-Alba AR (2010) Occurrence of emerging pollutants in urban wastewater and their removal through biological treatment followed by ozonation. Water Res 44:578–588CrossRefGoogle Scholar
  24. Santos JL, Aparicio I, Alonso E, Callejón M (2005) Simultaneous determination of pharmaceutically active compounds in wastewater samples by solid phase extraction and high-performance liquid chromatography with diode array and fluorescence detectors. Anal Chim Acta 550:116–122CrossRefGoogle Scholar
  25. 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
  26. Štrbac D, Aggelopoulos CA, Štrbac G, Dimitropoulos M, Novaković M, Ivetić T, Yannopoulos SN (2018) Photocatalytic degradation of naproxen and methylene blue: comparison between ZnO, TiO2 and their mixture. Process Saf Environ 113:174–183CrossRefGoogle Scholar
  27. Stumpf M, Ternes TA, Wilken RD, Rodrigues SV, Baumann W (1999) Polar drug residues in sewage and natural waters in the state of Rio de Janeiro, Brazil. Sci Total Environ 225:135–141CrossRefGoogle Scholar
  28. Tang YQ, Shi XT, Liu YZ, Feng L, Zhang LQ (2018) Degradation of clofibric acid in UV/chlorine disinfection process: kinetics, reactive species contribution and pathways. R Soc Open Sci 5(2):171372Google Scholar
  29. Tixier C, Singer HP, Oellers S, Müller SR (2003) Occurrence and fate of carbamazepine, clofibric acid, diclofenac, ibuprofen, ketoprofen, and naproxen in surface waters. Environ Sci Technol 37:1061–1068CrossRefGoogle Scholar
  30. Vieno NM, Härkki H, Tuhkanen T, Kronberg L (2007) Occurrence of pharmaceuticals in river water and their elimination in a pilot-scale drinking water treatment plant. Environ Sci Technol 41:5077–5084CrossRefGoogle Scholar
  31. Von Gunten U (2003) Ozonation of drinking water: part ii. Disinfection and by-product formation in presence of bromide, iodide or chlorine. Water Res 37:1469–1487CrossRefGoogle Scholar
  32. Wang TX, Margerum DW (2002) Kinetics of reversible chlorine hydrolysis: temperature dependence and general-acid/base-assisted mechanisms. Inorg Chem 33:1050–1055CrossRefGoogle Scholar
  33. Watts MJ, Linden KG (2007) Chlorine photolysis and subsequent OH radical production during UV treatment of chlorinated water. Water Res 41:2871–2878CrossRefGoogle Scholar
  34. Wu ZH, Fang JY, Xiang YY, Shang C, Li X, Meng FG, Yang X (2016) Roles of reactive chlorine species in trimethoprim degradation in the UV/chlorine process: kinetics and transformation pathways. Water Res 104:272–282CrossRefGoogle Scholar
  35. Yang Y, Pignatello JJ, Ma J, Mitch WA (2014) Comparison of halide impacts on the efficiency of contaminant degradation by sulfate and hydroxyl radical-based advanced oxidation processes (AOPs). Environ Sci Technol 48:2344–2351CrossRefGoogle Scholar
  36. Zhu YP, Wu M, Gao NY, Chu WH, Li K, Chen S (2018) Degradation of phenacetin by the UV/chlorine advanced oxidation process: kinetics, pathways, and toxicity evaluation. Chem Eng J 335:520–529CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Yongze Liu
    • 1
  • Yuqing Tang
    • 1
  • Yongxin Wu
    • 1
  • Li Feng
    • 1
    Email author
  • Liqiu Zhang
    • 1
  1. 1.Beijing Key Laboratory for Source Control Technology of Water Pollution, Engineering Research Center for Water Pollution Source Control and Eco-remediation, School of Environmental Science and EngineeringBeijing Forestry UniversityBeijingChina

Personalised recommendations