Environmental Science and Pollution Research

, Volume 23, Issue 19, pp 19096–19106 | Cite as

Photodegradation of the novel fungicide fluopyram in aqueous solution: kinetics, transformation products, and toxicity evolvement

  • Bizhang Dong
  • Jiye HuEmail author
Research Article


The aqueous photodegradation of fluopyram was investigated under UV light (λ ≥ 200 nm) and simulated sunlight irradiation (λ ≥ 290 nm). The effect of solution pH, fulvic acids (FA), nitrate (NO3 ), Fe (III) ions, and titanium dioxide (TiO2) on direct photolysis of fluopyram was explored. The results showed that fluopyram photodegradation was faster in neutral solution than that in acidic and alkaline solutions. The presence of FA, NO3 , Fe (III), and TiO2 slightly affected the photodegradation of fluopyram under UV irradiation, whereas the photodegradation rates of fluopyram with 5 mg L−1 Fe (III) and 500 mg L−1 TiO2 were about 7-fold and 13-fold faster than that without Fe (III) and TiO2 under simulated sunlight irradiation, respectively. Three typical products for direct photolysis of fluopyram have been isolated and characterized by liquid chromatography tandem mass spectrometry. These products resulted from the intramolecular elimination of HCl, hydroxyl-substitution, and hydrogen extraction. Based on the identified transformation products and evolution profile, a plausible degradation pathway for the direct photolysis of fluopyram in aqueous solution was proposed. In addition, acute toxicity assays using the Vibrio fischeri bacteria test indicated that the transformation products were more toxic than the parent compound.


Fluopyram Photodegradation Kinetics Transformation products Pathway Toxicity 

Supplementary material

11356_2016_7073_MOESM1_ESM.doc (384 kb)
ESM 1 (DOC 384 kb)


  1. Abellán MN, Bayarri B, Giménez J, Costa J (2007) Photocatalytic degradation of sulfamethoxazole in aqueous suspension of TiO2. Appl Catal B-Environ 74(3-4):233–41CrossRefGoogle Scholar
  2. Abramović BF, Banić ND, Šojić DV (2010) Degradation of thiacloprid in aqueous solution by UV and UV/H2O2 treatments. Chemosphere 81(1):114–9CrossRefGoogle Scholar
  3. Abramović BF, Despotović VN, Šojić DV, Orčić DZ, Csanádi JJ, Četojević-Simin DD (2013) Photocatalytic degradation of the herbicide clomazone in natural water using TiO2: Kinetics, mechanism, and toxicity of degradation products. Chemosphere 93(1):166–71CrossRefGoogle Scholar
  4. Antonopoulou M, Konstantinou I (2014) Photocatalytic treatment of metribuzin herbicide over TiO2 aqueous suspensions: removal efficiency, identification of transformation products, reaction pathways and ecotoxicity evaluation. J Photoch Photobio A 294:110–20CrossRefGoogle Scholar
  5. Avenot HF, Michailides TJ (2010) Progress in understanding molecular mechanisms and evolution of resistance to succinate dehydrogenase inhibiting (SDHI) fungicides in phytopathogenic fungi. Crop Prot 29:643–51CrossRefGoogle Scholar
  6. Avetta P, Marchetti G, Minella M, Pazzi M, Laurentiis E, Maurino V, Minero C, Vione D (2014) Phototransformation pathways of the fungicide dimethomorph ((E, Z)4-[3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)-1-oxo-2-propenyl] morpholine), relevant to sunlit surface waters. Sci Total Environ 500–501:351–60CrossRefGoogle Scholar
  7. Canle LM, Fernández MI, Santaballa JA (2005) Developments in the mechanism of photodegradation of triazine-based pesticides. J Phys Org Chem 18(2):148–55CrossRefGoogle Scholar
  8. Cao G, Lu J, Wang G (2012) Photolysis kinetics and influencing factors of bisphenol S in aqueous solutions. J Environ Sci 24(5):846–51CrossRefGoogle Scholar
  9. Chen Y, Zhang K, Zuo YG (2013) Direct and indirect photodegradation of estriol in the presence of humic acid, nitrate and iron complexes in water solutions. Sci Total Environ 463(5):802–9CrossRefGoogle Scholar
  10. Conceição M, Mateus DA, Silva AM, Burrows HD (1994) Environmental and laboratory studies of the photodegradation of the pesticide fenarimol. J Photoch Photobio A 80(1-3):409–16CrossRefGoogle Scholar
  11. De Miccolis Angelini RM, Masiello M, Rotolo C, Pollastro S, Faretra F (2014) Molecular characterisation and detection of resistance to succinate dehydrogenase inhibitor fungicides in Botryotinia fuckeliana (Botrytis cinerea). Pest Manag Sci 70(12):1884–93CrossRefGoogle Scholar
  12. Doll TE, Frimmel FH (2005) Photocatalytic degradation of carbamazepine, clofibric acid and iomeprol with P25 and Hombikat UV100 in the presence of natural organic matter (NOM) and other organic water constituents. Water Res 39:403–11CrossRefGoogle Scholar
  13. Dong BZ, Hu JY (2014) Dissipation and residue determination of fluopyram and tebuconazole residues in watermelon and soil by GC-MS. Int J Environ An Ch 94(5):493–505CrossRefGoogle Scholar
  14. Escher BI, Fenner K (2011) Recent advances in environmental risk assessment of transformation products. Environ Sci Technol 45(9):3835–47CrossRefGoogle Scholar
  15. Espinoza LAT, Neamtu M, Frimmel FH (2007) The effect of nitrate, Fe(III) and bicarbonate on the degradation of bisphenol A by simulated solar UV irradiation. Water Res 41:4479–87CrossRefGoogle Scholar
  16. European Food Safety Authority (2011) Setting of new MRLs and import tolerances for fluopyram in various crops. EFSA J 9(9):2388CrossRefGoogle Scholar
  17. 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(1-2):167–74CrossRefGoogle Scholar
  18. Filipe OMS, Santos SAO, Domingues MRM, Vidal MM, Silvestre AJD, Neto CP, Santos EBH (2013) Photodegradation of the fungicide thiram in aqueous solutions. Kinetic studies and identification of the photodegradation products by HPLC-MS/MS. Chemosphere 91:993–1001CrossRefGoogle Scholar
  19. Fisher JM, Reese JG, Pellechia PJ, Moeller PL, Ferry JL (2006) Role of Fe(III), phosphate, dissolved organic matter, and nitrate during the photodegradation of domoic acid in the marine environment. Environ Sci Technol 40:2200–5CrossRefGoogle Scholar
  20. Grabowska E, Reszczynska J, Zaleska A (2012) Mechanism of phenol photodegradation in the presence of pure and modified-TiO2: a review. Water Res 46(17):5453–71CrossRefGoogle Scholar
  21. Guan WB, Ma Y, Zhang HY (2012) Residue and dissipation dynamics of fluopyram in cucumber and soil. Adv Mater Res 347–353:2255–9Google Scholar
  22. Health Canada Pest Management Regulatory Agency (2014) Evaluation report- ERC 2014-02: fluopyram. 2-7Google Scholar
  23. Hoff RB, Meneghini L, Pizzolato TM, Peralba MC, Díaz-Cruz MS, Barceló D (2014) Structural elucidation of sulfaquinoxaline metabolism products and their occurrence in biological samples using high-resolution Orbitrap mass spectrometry. Anal Chem 86(11):5579–86CrossRefGoogle Scholar
  24. Ishii H, Miyamoto T, Ushio S, Kakishima M (2011) Lack of cross-resistance to a novel succinate dehydrogenase inhibitor, fluopyram, in highly boscalid-resistant isolates of Corynespora cassiicola and Podosphaera xanthii. Pest Manag Sci 67(4):474–82CrossRefGoogle Scholar
  25. Jiao S, Zheng S, Yin D, Wang L, Chen L (2008) Aqueous photolysis of tetracycline and toxicity of photolytic products to luminescent bacteria. Chemosphere 73:377–82CrossRefGoogle Scholar
  26. Kim T, Kim J, Choi K, Stenstrom MK, Zoh K (2006) Degradation mechanism and the toxicity assessment in TiO2 photocatalysis and photolysis of parathion. Chemosphere 62(6):926–33CrossRefGoogle Scholar
  27. Kumar V, Upadhay N, Wasit AB, Singh S (2013) Spectroscopic methods for the detection of organophosphate pesticides—a preview. Current World Environ 8(2):313–8CrossRefGoogle Scholar
  28. Lavtizăr V, van Gestel CAM, Dolenc D, Trebše P (2014) Chemical and photochemical degradation of chlorantraniliprole and characterization of its transformation products. Chemosphere 95:408–14CrossRefGoogle Scholar
  29. Labourdette G, Lachaise H, Rieck H, Steiger D (2010) Fluopyram: a new antifungal agent for the control of problematic plant diseases of many crops. Julius-Kühn-Arch 428:91–2Google Scholar
  30. Lambropoulou DA, Konstantinou IK, Albanis TA, Fernández-Alba AR (2011) Photocatalytic degradation of the fungicide fenhexamid in aqueous TiO2 suspensions: identification of intermediates products and reaction pathways. Chemosphere 83(3):367–78CrossRefGoogle Scholar
  31. Li Y, Niu JF, Wang WL (2011) Photolysis of Enrofloxacin in aqueous systems under simulated sunlight irradiation: kinetics, mechanism and toxicity of photolysis products. Chemosphere 85(5):892–7CrossRefGoogle Scholar
  32. Liu P, Xu Y, Li J, Liu J, Cao Y, Liu X (2012) Photodegradation of the isoxazolidine fungicide SYP-Z048 in aqueous solution: kinetics and photoproducts. J Agric Food Chem 60(47):11657–63CrossRefGoogle Scholar
  33. Liu N, Sijak S, Zheng M, Tang L, Xu G, Wu M (2015) Aquatic photolysis of florfenicol and thiamphenicol under direct UV irradiation, UV/H2O2, and UV/Fe (II) processes. Chem Eng J 260:826–34CrossRefGoogle Scholar
  34. Liu W, Chen SF, Zhao W, Zhang SJ (2009) Titanium dioxide mediated photocatalytic degradation of methamidophos in aqueous phase. J Hazard Mater 164(1):154–60CrossRefGoogle Scholar
  35. Liu Y, Lan XF, Gao XM, Shen ZH, Lu J, Ni XW (2002) Study of acetic acid spectral characteristics. Applied Laser 22(6):559–62, In ChineseGoogle Scholar
  36. Mao L, Meng C, Zeng C, Ji YF, Yang X, Gao SX (2011) The effect of nitrate, bicarbonate and natural organic matter on the degradation of sunscreen agent p-aminobenzoic acid by simulated solar irradiation. Sci Total Environ 409(24):5376–81CrossRefGoogle Scholar
  37. Martínez-Zapata M, Aristizábal C, Peñuela G (2013) Photodegradation of the endocrine-disrupting chemicals 4 n -nonylphenol and triclosan by simulated solar UV irradiation in aqueous solutions with Fe(III) and in the absence/presence of humic acids. J Photoch Photobiolo A 251(9):41–9CrossRefGoogle Scholar
  38. Martínez Vidal JL, Plaza-Bolaños P, Romero-González R, Garrido FA (2009) Determination of pesticide transformation products: a review of extraction and detection methods. J Chromatogr A 1216:6767–88CrossRefGoogle Scholar
  39. Meng F-J, Ni Z-L, Wu C-J (2002) Nitrate concentrations in drinking water. Foreign Medcbtm Sci (Section of Medgeography) 23(3):115–6 (In Chinese)Google Scholar
  40. Niu J, Zhang L, Li Y, Zhao J, Lv S, Xiao K (2013) Effects of environmental factors on sulfamethoxazole photodegradation under simulated sunlight irradiation: kinetics and mechanism. J Environ Sci 25(6):1098–106CrossRefGoogle Scholar
  41. Pinna MV, Pusino A (2012) Direct and indirect photolysis of two quinolinecarboxylic herbicides in aqueous systems. Chemosphere 86(6):655–8CrossRefGoogle Scholar
  42. Robert D, Malato S (2002) Solar photocatalysis: a clean process for water detoxification. Sci Total Environ 291:85–97CrossRefGoogle Scholar
  43. Sanches S, Crespo MT, Pereira VJ (2010) Drinking water treatment of priority pesticides using low pressure UV photolysis and advanced oxidation processes. Water Res 44(6):1809–18CrossRefGoogle Scholar
  44. Sandín-España P, Sevilla-Morán B, Calvo L, Mateo-Miranda M, Alonso-Prados JL (2013) Photochemical behavior of alloxydim herbicide in environmental waters. Structural elucidation and toxicity of degradation products. Microchem J 106:212–9CrossRefGoogle Scholar
  45. Sevilla-Morán B, López-Goti C, Alonso-Prados JL, Sandín-España P (2014) Aqueous photodegradation of sethoxydim herbicide: Qtof elucidation of its by-products, mechanism and degradation pathway. Sci Total Environ 472:842–50CrossRefGoogle Scholar
  46. Shi X, Zhang R, Zhang H, Xu F, Zhang Q, Wang W (2015) Influence of water on the homogeneous gas-phase formation mechanism of polyhalogenated dioxins/furans from chlorinated/brominated phenols as precursors. Chemosphere 137:142–8CrossRefGoogle Scholar
  47. Sinclair CJ (2009) Predicting the environmental fate and ecotoxicological and toxicological effects of pesticide transformation products. Dissertation, University of YorkGoogle Scholar
  48. Sinclair CJ, Boxall ABA (2003) Assessing the ecotoxicity of pesticide transformation products. Environ Sci Technol 37:4617–25CrossRefGoogle Scholar
  49. Tan C, Gao N, Zhou S, Zhuang Z (2014) Kinetic study of acetaminophen degradation by UV-based advanced oxidation processes. Chem Eng J 253(7):229–36CrossRefGoogle Scholar
  50. Tong L, Eichhorn P, Pérez S, Wang Y, Barceló D (2011) Photodegradation of azithromycin in various aqueous systems under simulated and natural solar radiation: kinetics and identification of photoproducts. Chemosphere 83:340–8CrossRefGoogle Scholar
  51. Torrents A, Anderson BG, Bilboulian S, Johnson WE, Hapeman CJ (1997) Atrazine photolysis: mechanistic investigations of direct and nitrate-mediated hydroxy radical processes and the influence of dissolved organic carbon from the chesapeake bay. Environ Sci Technol 31(5):1476–82CrossRefGoogle Scholar
  52. USEPA (2008) Fate, transport and transformation test guidelines. OPPTS 835.2120, Hydrolysis. EPA 712-C-08-012Google Scholar
  53. Veloukas T, Karaoglanidis GS (2012) Biological activity of the succinatedehydrogenase inhibitor fluopyram against Botrytis cinerea and fungal baseline sensitivity. Pest Manag Sci 68(6):85–864CrossRefGoogle Scholar
  54. Wang J, Zhou T, Mao J, Wu X (2015) Comparative study of sulfamethazine degradation in visible light induced photo-Fenton and photo-Fenton-like systems. J Environ Chemical Eng 3(1):2393–400CrossRefGoogle Scholar
  55. Wang L, Zhang CB, Wu F, Deng NS, Glebov EM, Bazhin NM (2006) Determination of hydroxyl radicals from photolysis of Fe(III)-pyruvate complexes in homogeneous aqueous solution. React Kinet Catal L 89(1):183–92CrossRefGoogle Scholar
  56. Wu F, Deng NS (2000) Photochemistry of hydrolytic iron (III) species and photoinduced degradation of organic compounds. A mini review. Chemosphere 41:1137–47CrossRefGoogle Scholar
  57. Xia XH, Li GC, Yang ZF, Chen YM, Huang GH (2009) Effects of fulvic acid concentration and origin on photodegradation of polycyclic aromatic hydrocarbons in aqueous solution: importance of active oxygen. Environ Pollut 157(4):1352–9CrossRefGoogle Scholar
  58. Xie JM, Wang PL, Liu J, Lv XM, Jiang DL, Sun C (2011) Photodegradation of lambda-cyhalothrin and cypermethrin in aqueous solution as affected by humic acid and/or copper: intermediates and degradation pathways. Environ Toxicol Chem 30(11):2440–8CrossRefGoogle Scholar
  59. Xu J, Hao Z, Guo C, Zhang Y, He Y, Meng W (2014) Photodegradation of sulfapyridine under simulated sunlight irradiation: kinetics, mechanism and toxicity evolvement. Chemosphere 99(3):186–91CrossRefGoogle Scholar
  60. Yan G, Sun H, Sun W, Zhao L, Meng X, Wang X (2010) Rapid and global detection and characterization of aconitum alkaloids in Yin Chen Si Ni Tang, a traditional Chinese medical formula, by ultra performance liquid chromatography-high resolution mass spectrometry and automated data analysis. J Pharmaceut Biomed 53:421–31CrossRefGoogle Scholar
  61. Yang Y, Yin XJ, Guo HM, Wang RL, Song R, Tian Y, Zhang ZJ (2014) Identification and comparative analysis of the major chemical constituents in the extracts of single Fuzi herb and Fuzi-Gancao herb-pair by UFLC-IT-TOF/MS. Chin J Nat Med 12(7):542–53Google Scholar
  62. Zhang Y, Xu J, Dong FS, Liu XG, Wu XH, Zheng YQ (2014) Response of microbial community to a new fungicide fluopyram in the silty-loam agricultural soil. Ecotox Environ Safe 108:273–80CrossRefGoogle Scholar
  63. Zhou JH (2006) The application of the high content of iron ions in groundwater for boiler feed water. China Special Equipment Safety 22(1):37–8 (In Chinese)Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2016

Authors and Affiliations

  1. 1.Laboratory of Pesticide Residues and Environmental Toxicology, School of Chemistry and Biological EngineeringUniversity of Science and Technology BeijingBeijingPeople’s Republic of China

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