Endocrine Activities of Pesticides During Ozonation of Waters

  • Paul Westlund
  • Siavash Isazadeh
  • Alexandre Therrien
  • Viviane Yargeau


Two yeast-based bioassays were used to assess the endocrine activity potential of transformation products formed during the ozonation of water containing a variety of pesticides (propiconazole, atrazine, 2,4-dichlorophenoxyacetic acid [2,4-D], tebuconazole, climbazole, myclobutanil, irgarol, terbutryn, dicamba, mecoprop and diuron). Ozone experiments were conducted first in reverse osmosis water to isolate the effects of the pesticides and then in synthetic wastewater and wastewater effluent to investigate whether the results translated to more complex matrices. The findings demonstrate the recalcitrant nature of most pesticides during ozonation, with removals below 50%, except for irgarol, terbutryn and climbazole with removals up to 70%. This study is the first one to investigate the removal of the fungicides myclobutanil and tebuconazole by ozonation and is one of the first studies to investigate the androgenic activity of ozonation transformation products of contaminants of emerging concern. These findings also demonstrated that during ozonation the initial anti-androgenic activity was removed while the estrogenic activity remained undetected and the androgenic activity increased to levels up to 60% of the anti-androgenic activity of the DHT control. These results indicate that bioactivity should be considered in the evaluation of treatment performance and risks assessment associated to wastewater discharges.


Ozonation Transformation products Estrogenic activity Androgenic activity Pesticides 



Funding for this study was provided by a research grant to Viviane Yargeau (PI) from the Natural Sciences and Engineering Research Council (NSERC) of Canada through the Discovery Grant Program (RGPIN/04635-2015) and by the McGill Engineering Doctoral Award (MEDA).


  1. Chu W, Chan KH, Kwan CY (2004) Modeling the ozonation of herbicide 2,4-D through a kinetic approach. Chemosphere 55:647–652CrossRefGoogle Scholar
  2. de Oliveira PR, Lopez de Alda M, Joglar J, Daniel LA, Barceló D (2011) Identification of new ozonation disinfection byproducts of 17 [beta]-estradiol and estrone in water. Chemosphere 84.
  3. Ikehata K, Gamal El-Din M (2005a) Aqueous pesticide degradation by ozonation and ozone-based advanced oxidation processes: a review (part I) ozone. Sci Eng 27:83–114Google Scholar
  4. Ikehata K, Gamal El-Din M (2005b) Aqueous pesticide degradation by ozonation and ozone-based advanced oxidation processes: a review (part II) ozone. Sci Eng 27:173–202Google Scholar
  5. Klamerth N, Rizzo L, Malato S, Maldonado MI, Agüera A, Fernández-Alba AR (2010) Degradation of fifteen emerging contaminants at μg L-1 initial concentrations by mild solar photo-Fenton in MWTP effluents. Water Res 44:545–554. CrossRefGoogle Scholar
  6. Kuang J, Huang J, Wang B, Cao Q, Deng S, Yu G (2013) Ozonation of trimethoprim in aqueous solution: identification of reaction products and their toxicity. Water Res 47:2863–2872. CrossRefGoogle Scholar
  7. Larcher S, Delbes G, Robaire B, Yargeau V (2012) Degradation of 17alpha-ethinylestradiol by ozonation-identification of the by-products and assessment of their estrogenicity and toxicity. Environ Int 39:66–72. CrossRefGoogle Scholar
  8. Lassonde G, Nasuhoglu D, Pan JF, Gaye B, Yargeau V, Delbes G (2015) Ozone treatment prevents the toxicity of an environmental mixture of estrogens on rat fetal testicular development. Reprod Toxicol 58:85–92. CrossRefGoogle Scholar
  9. Margot J et al (2013) Treatment of micropollutants in municipal wastewater: ozone or powdered activated carbon? Sci Total Environ 461–462:480–498 CrossRefGoogle Scholar
  10. Mehrjouei M, Müller S, Möller D (2015) A review on photocatalytic ozonation used for the treatment of water and wastewater. Chem Eng J 263:209–219. CrossRefGoogle Scholar
  11. Meijers RT, Oderwald-Muller EJ, Kruithof JC (1995) Degradation of pesticides by ozonation and advanced oxidation ozone. Sci Eng 17:673–686. Google Scholar
  12. Ormad MP, Miguel N, Lanao M, Mosteo R, Ovelleiro JL (2010) Effect of application of ozone and ozone combined with hydrogen peroxide and titanium dioxide in the removal of pesticides from water ozone. Sci Eng 32:25–32Google Scholar
  13. Paraskeva P, Graham NJ (2002) Ozonation of municipal wastewater effluents. Water Environ Res 74:569–581CrossRefGoogle Scholar
  14. 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. CrossRefGoogle Scholar
  15. Santiago-Morales J, Gómez MJ, Herrera S, Fernández-Alba AR, García-Calvo E, Rosal R (2012) Oxidative and photochemical processes for the removal of galaxolide and tonalide from wastewater. Water Res 46:4435–4447. CrossRefGoogle Scholar
  16. Segura PA, Kaplan P, Yargeau V (2013) Identification and structural elucidation of ozonation transformation products of estrone. Chem Cent J 7:1–11. CrossRefGoogle Scholar
  17. Shang NC, Yu YH, Ma HW (2002) Variation of toxicity during the ozonation of monochlorophenolic solutions. J Environ Sci Health A Tox Hazard Subst Environ Eng 37:261–271CrossRefGoogle Scholar
  18. Snyder SA, Wert EC, Rexing DJ, Zegers RE, Drury DD (2006) Ozone oxidation of endocrine disruptors and pharmaceuticals in surface water and wastewater ozone. Sci Eng 28:445–460. Google Scholar
  19. Sohoni P, Sumpter J (1998) Several environmental oestrogens are also anti-androgens. J Endocrinol 158:327–339CrossRefGoogle Scholar
  20. Solís RR, Rivas FJ, Martínez-Piernas A, Agüera A (2016) Ozonation, photocatalysis and photocatalytic ozonation of diuron intermediates identification. Chem Eng J 292:72–81 CrossRefGoogle Scholar
  21. Sui Q et al (2014) Removal of pharmaceutical and personal care products by sequential ultraviolet and ozonation process in a full-scale wastewater treatment plant. Front Environ Sci Eng 8:62–68. CrossRefGoogle Scholar
  22. Westlund P,  Isazadeh S, Yargeau V (2018) Investigating the androgenic activity of ozonation transformation products of testosterone and androstenedione. J Hazard Mater 342:492–498.
  23. Westlund P, Yargeau V (2017) Investigation of the presence and endocrine activities of pesticides found in wastewater effluent using yeast-based bioassays. Sci Total Environ 607–608:744–751. CrossRefGoogle Scholar
  24. Yang Y, Cao H, Peng P, Bo H (2014) Degradation and transformation of atrazine under catalyzed ozonation process with TiO2 as catalyst. J Hazard Mater 279:444–451 doi. CrossRefGoogle Scholar
  25. Yargeau V, Danylo F (2015) Removal and transformation products of ibuprofen obtained during ozone- and ultrasound-based oxidative treatment. Water Sci Technol 72:491–500. CrossRefGoogle Scholar
  26. Zhou Q, Ding Y, Xiao J, Liu G, Guo X (2007) Investigation of the feasibility of TiO(2) nanotubes for the enrichment of DDT and its metabolites at trace levels in environmental water samples. J Chromatogr A 1147:10–16CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2017

Authors and Affiliations

  1. 1.Department of Chemical EngineeringMcGill UniversityMontrealCanada

Personalised recommendations