Transformation of atrazine by photolysis and radiolysis: kinetic parameters, intermediates and economic consideration

  • Georgina Rózsa
  • Ákos Fazekas
  • Máté Náfrádi
  • Tünde Alapi
  • Krisztina Schrantz
  • Erzsébet TakácsEmail author
  • László Wojnárovits
  • Andreas Fath
  • Thomas Oppenländer
Research Article


Four techniques, UV254 nm photolysis, vacuum ultraviolet (VUV172 nm) photolysis, combined UV254 nm/VUV185 nm photolysis and gamma (γ) radiolysis were used to induce the transformation of atrazine in aqueous solution. The effects of dissolved oxygen (atrazine concentration 1 × 10−4 mol L−1 and 4.6 × 10−7 mol L−1) and matrix (high purity water/purified wastewater, atrazine concentration 4.6 × 10−7 mol L−1) and the electric energy requirements were investigated. The calculation of the energy input in cases of the photolyses was based on the lamp’s power. In radiolysis, the absorbed dose (J kg−1) was the basis. In UV photolysis, atrazine transforms to atrazine-2-hydroxy; this product practically does not degrade during UV photolysis; due to this reason, the mineralisation is very slow. This and some other products of atrazine decomposition degrade only in radical reactions. Dissolved oxygen usually slightly enhances the degradation rate. At 10−7 mol L−1 concentration level, the matrix, high purity water/purified wastewater, has not much influence on the degradation rates in UV photolysis and radiolysis. In the VUV and UV/VUV systems, considerable matrix effects were observed. Comparing the electric energy requirements of the four degradation processes, radiolysis was found to be the economically most feasible method, requiring 1–2 orders of magnitude less electric energy than UV/VUV, VUV and UV photolysis.


Atrazine AOPs Hydroxyl radical Hydrated electron Mineralisation Intermediates Energy requirements 


Funding information

This research was supported by OTKA, NK 105802. T. Alapi and K. Schrantz acknowledge the German Academic Exchange Service (DAAD) and Tempus Foundation for financial support (project number: 151955). K. Schrantz acknowledges the European Union and the State of Hungary, co-financed by the European Social Fund in the framework of TÁMOP 4.2.4. A/1-11-1-2012-0001 ‘National Excellence Program’.


  1. Alapi T, Dombi A (2007) Comparative study of the UV and UV/VUV-induced photolysis of phenol in aqueous solution. J Photochem Photobiol A Chem 188:409–418CrossRefGoogle Scholar
  2. Alapi T, Schrantz K, Arany E, Kozmér Zs (2017) Vacuum UV driven processes. In: Stefan MI (ed) Advanced oxidation processes for water treatment. IWA Publishing, London, pp 195–239Google Scholar
  3. Al-Gharabli S, Engeßer P, Gera D, Klein S, Oppenländer T (2016) Engineering of a highly efficient Xe2 -excilamp (xenon excimer lamp, λmax = 172 nm, η = 40%) and qualitative comparison to a low-pressure mercury lamp (PL-Hg, λ = 185/254 nm) for water purification. Chemosphere 144:811–815CrossRefGoogle Scholar
  4. Angelini G, Bucci R, Carnevaletti F, Colosimo M (2000) Radiolytic decomposition of aqueous atrazine. Radiat Phys Chem 59:303–307CrossRefGoogle Scholar
  5. 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
  6. Azenha MEDG, Burrows HD, Canle LM, Coimbra R, Fernández MI, García MV, Peiteado MA, Santaballa JA (2003) Kinetic and mechanistic aspects of the direct photodegradation of atrazine, atraton, ametryn and 2-hydroxyatrazine by 254 nm light in aqueous solution. J Phys Org Chem 16:498–503CrossRefGoogle Scholar
  7. Baranda A, Barranco A, de Marañón IM (2011) Fast atrazine photodegradation in water by pulsed light technology. Water Res 46:669–678CrossRefGoogle Scholar
  8. Basfar AA, Mohamed KA, Al-Abduly AJ, Al-Shahrani AA (2009) Radiolytic degradation of atrazine aqueous solution containing humic substances. Ecotoxicol Environ Saf 72:948–953CrossRefGoogle Scholar
  9. Buxton GV (2004) The radiation chemistry of liquid water: principles and applications. In: Mozumder A, Hatano Y (eds) Charged particle and photon interaction with matter. Marcel Dekker, New York, pp 331–365Google Scholar
  10. Buxton GV, Greenstock CL, Helman WP, Ross BA (1988) Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (OH/O) in aqueous solution. J Phys Chem Ref Data 17:513–886CrossRefGoogle Scholar
  11. Chen C, Yang S, Guo Y, Sun C, Gu C, Xu B (2009) Photolytic destruction of endocrine disruptor atrazine in aqueous solution under UV irradiation: products and pathways. J Hazard Mater 172:675–684CrossRefGoogle Scholar
  12. Chramosta N, De Laat J, Dore M, Suty H, Pouillot M (1993) Rate constants for reaction of hydroxyl radicals with S-triazines. Environ Technol 14:215–226CrossRefGoogle Scholar
  13. Dao YH, De Laat J (2011) Hydroxyl radical involvement in the decomposition of hydrogen peroxide by ferrous and ferric-nitrilotriacetate complexes at neutral pH. Water Res 45:3309–3317CrossRefGoogle Scholar
  14. De Laat J, Lebarbier R, Chramosta N, Dore M (1994) Reactivity of 2-chloro-, 2-methoxy- and 2-methylthio s-triazines towards hydroxyl radicals. J Eur Hydrol 25:185–198Google Scholar
  15. Gallard H, De Laat J (2001) Kinetics of oxidation of chlorobenzenes and phenyl-ureas by Fe(II)/H2O2 and Fe(III)/H2O2. Evidence of reduction and oxidation reactions of intermediates by Fe(II) or Fe(III). Chemosphere 42:405–413CrossRefGoogle Scholar
  16. Gonzalez MC, Braun AM, Prevot AB, Pelizzetti E (1994) Vacuum-ultraviolet (VUV) photolysis of water: mineralization of atrazine. Chemosphere 28:2121–2127CrossRefGoogle Scholar
  17. Graymore M, Stagnitti F, Allinson G (2001) Impacts of atrazine in aquatic ecosystems. Environ Int 26:483–495CrossRefGoogle Scholar
  18. Haag WR, Yao CCD (1992) Rate constants for reaction of hydroxyl radicals with several drinking water contaminants. Environ Sci Technol 26:1005–1013CrossRefGoogle Scholar
  19. Hatchard CG, Parker CA, Bowen EJ (1956) A new sensitive chemical actinometer - II. Potassium ferrioxalate as a standard chemical actinometer. Proc R Soc Lond Math Phys Sci A235:518–536Google Scholar
  20. Heit G, Neuner A, Saugy P-Y, Braun AM (1998) Vacuum-UV (172 nm) actinometry. The quantum yield of the photolysis of water. J Phys Chem A 102:5551–5561CrossRefGoogle Scholar
  21. Hirt RC, Halverson F, Schmitt RG (1954) S-Triazine: II. The near ultraviolet absorption spectrum. J Chem Phys 22:1148–1149CrossRefGoogle Scholar
  22. Horikoshi S, Hidaka H (2003) Non-degradable triazine substrates of atrazine and cyanuric acid hydrothermally and in supercritical water under the UV-illuminated photocatalytic cooperation. Chemosphere 51:139–142CrossRefGoogle Scholar
  23. Hussein SY, El-Nasser MA, Ahmed SM (1996) Comparative studies on the effects of herbicide atrazine on freshwater fish Oreochromis niloticus and Chrysichthyes auratus at Assiut, Egypt. Bull Environ Contam Toxicol 57:503–510CrossRefGoogle Scholar
  24. IAEA (2007) Radiation processing, environmental applications. International Atomic Energy Agency, ViennaGoogle Scholar
  25. Karpel VLN, Berger P, Gehringer P (1998) γ-Irradiation for the removal of atrazine in aqueous solution containing humic substances. Radiat Phys Chem 55:317–322CrossRefGoogle Scholar
  26. Khan JA (2013) Removal of atrazine from aqueous solution using advanced oxidation techniques. Dissertation. University of Peshawar, PeshawarGoogle Scholar
  27. Khan JA, He X, Shah NS, Sayed M, Khan HM, Hapeshi E, Fatta-Kassinos D, Dionysiou DD (2014) Kinetic and mechanism investigation on the photochemical degradation of atrazine with activated H2O2, S2O8 2− and HSO5. Chem Eng J 252:393–403CrossRefGoogle Scholar
  28. Khan JA, He X, Shah NS, Sayed M, Khan HM, Dionysiou DD (2017) Degradation kinetics and mechanism of desethyl-atrazine and desisopropyl-atrazine in water with OH and SO4 •- based AOPs. Chem Eng J 325:485–494CrossRefGoogle Scholar
  29. Kozmér Z, Arany E, Alapi T, Takács E, Wojnárovits L, Dombi A (2014) Determination of the rate constant of hydroperoxyl radical reaction with phenol. Radiat Phys Chem 102:135–138CrossRefGoogle Scholar
  30. Lawton JC, Pennington PL, Chung KW, Scott GI (2006) Toxicity of atrazine to the juvenile hard clam, Mercenaria mercenaria. Ecotoxicol Environ Saf 65:388–394CrossRefGoogle Scholar
  31. Loosli R (1994) Triazines. Toxicol 91:59–62CrossRefGoogle Scholar
  32. Mabury SA, Crosby DG (1994) The relationship of hydroxyl reactivity to pesticide persistence. In: Helz GR, Zepp RG, Crosby DG (eds) Aquatic and surface photochemistry. CRC Press, Inc, Boca Raton, pp 149–161Google Scholar
  33. Mora AS, Mohseni M (2018) Temperature dependence of the absorbance of 185 nm photons by water and commonly occurring solutes and its influence on the VUV advanced oxidation process. Environ Sci Water Res Technol 4:1303–1309CrossRefGoogle Scholar
  34. Moreira AJ, Borges AC, Gouvea LFC, MacLeod TCO, Freschi GPG (2017) The process of atrazine degradation, its mechanism, and the formation of metabolites using UV and UV/MW photolysis. J Photochem Photobiol A Chem 347:160–167CrossRefGoogle Scholar
  35. Omran NE, Salama WM (2016) The endocrine disruptor effect of the herbicides atrazine and glyphosate on Biomphalaria alexandrina snails. Toxicol Ind Health 32:656–665CrossRefGoogle Scholar
  36. Oppenländer T (2003) VUV and UV radiant sources and their characteristics. In: Oppenländer T (ed) Photochemical purification of water and air. Wiley-VCH Verlag GmbH&co. KGaA, Weinheim, pp 79–100Google Scholar
  37. Oppenländer T, Schwarzwälder R (2002) Vacuum-UV oxidation (H2O-VUV) with a xenon excimer flow-through lamp at 172 nm: use of methanol as actinometer for VUV intensity measurement and as reference compound for OH-radical competition kinetics in aqueous systems. J Adv Oxid Technol 5:155–163Google Scholar
  38. Parra S, Stanca SE, Guasaquillo I, Thampi KR (2004) Photocatalytic degradation of atrazine using suspended and supported TiO2. Appl Catal B Environ 51:107–116CrossRefGoogle Scholar
  39. Reh R, Licha T, Geyer T, Nodler K, Sauter M (2013) Occurrence and spatial distribution of organic micro-pollutants in a complex hydrogeological karst system during low flow and high flow periods, results of a two-year study. Sci Total Environ 443:438–445CrossRefGoogle Scholar
  40. Samardzija D, Pogrmic-Majkic K, Fa S, Glisic B, Stanic B, Andric N (2016) Atrazine blocks ovulation via suppression of Lhr and Cyp19a1 mRNA and estradiol secretion in immature gonadotropin-treated rats. Reprod Toxicol 61:10–18CrossRefGoogle Scholar
  41. Sass JB, Colangelo A (2006) European Union bans atrazine, while the United States negotiates continued use. Int J Occup Environ Health 12:260–267CrossRefGoogle Scholar
  42. Solomon KR, Baker DB, Richards RP, Dixon KR, Klaine SJ, Lapoint TW, Kendall RJ, Weisskopf CP, Giddings JM, Giesy JP, Hall LW, Williams WM (1996) Ecological risk assessment of atrazine in North American surface waters. Environ Toxicol Chem 15:31–76CrossRefGoogle Scholar
  43. Sousa JCG, Ribeiro AR, Barbosa MO, Pereira MFR, Silva AMT (2018) A review on environmental monitoring of water organic pollutants identified by EU guidelines. J Hazard Mater 344:146–162CrossRefGoogle Scholar
  44. Spinks JWT, Woods RJ (1990) An introduction to radiation chemistry, 3rd edn. Wiley-Interscience, New-YorkGoogle Scholar
  45. Tauber A, von Sonntag C (2000) Products and kinetics of the OH-radical-induced dealkylation of atrazine. Acta Hydrochim Hydrobiol 28:15–23CrossRefGoogle Scholar
  46. Varghese R, Mohan H, Manoj P, Manoj VM, Aravind UK, Vandana K, Aravindakumar CT (2006) Reactions of hydrated electrons with triazine derivatives in aqueous medium. J Agric Food Chem 54:8171–8176CrossRefGoogle Scholar
  47. Ventura A, Jacquet G, Bermond A, Camel V (2002) Electrochemical generation of the Fenton's reagent: application to atrazine degradation. Water Res 36:3517–3522CrossRefGoogle Scholar
  48. Weeks JL, Meaburn GMAC, Gordon S (1963) Absorption coefficients of liquid water and aqueous solutions in the far ultraviolet. Radiat Res 19:559–567CrossRefGoogle Scholar
  49. Wojnárovits L, Takács E (2014) Rate coefficients of hydroxyl radical reactions with pesticide molecules and related compounds: a review. Radiat Phys Chem 96:120–134CrossRefGoogle Scholar
  50. Wojnárovits L, Takács E, Szabó L (2017) Gamma-ray and electron beam-based AOPs. In: Stefan MI (ed) Advanced oxidation processes for water treatment. IWA Publishing, London, pp 241–296 ISBN: 97817804071280Google Scholar

Copyright information

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

Authors and Affiliations

  • Georgina Rózsa
    • 1
    • 2
  • Ákos Fazekas
    • 1
  • Máté Náfrádi
    • 1
  • Tünde Alapi
    • 1
  • Krisztina Schrantz
    • 1
  • Erzsébet Takács
    • 2
    Email author
  • László Wojnárovits
    • 2
  • Andreas Fath
    • 3
  • Thomas Oppenländer
    • 3
  1. 1.Department of Inorganic and Analytical ChemistryUniversity of SzegedSzegedHungary
  2. 2.Radiation Chemistry Department, Institute for Energy Security and Environmental Safety, Centre for Energy ResearchHungarian Academy of SciencesBudapestHungary
  3. 3.Faculty of Medical and Life SciencesHochschule Furtwangen University, Campus Villingen-SchwenningenVillingen-SchwenningenGermany

Personalised recommendations