Advertisement

Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Photodegradation of gemfibrozil in aqueous solution under UV irradiation: kinetics, mechanism, toxicity, and degradation pathways

  • 770 Accesses

  • 10 Citations

Abstract

The lipid regulator gemfibrozil (GEM) has been reported to be persistent in conventional wastewater treatment plants. This study investigated the photolytic behavior, toxicity of intermediate products, and degradation pathways of GEM in aqueous solutions under UV irradiation. The results demonstrated that the photodegradation of GEM followed pseudo-first-order kinetics, and the pseudo-first-order rate constant was decreased markedly with increasing initial concentrations of GEM and initial pH. The photodegradation of GEM included direct photolysis via 3GEM* and self-sensitization via ROS, where the contribution rates of degradation were 0.52, 90.05, and 8.38 % for ·OH, 1O2, and 3GEM*, respectively. Singlet oxygen (1O2) was evidenced by the molecular probe compound, furfuryl alcohol (FFA), and was identified as the primary reactive species in the photolytic process. The steady-state concentrations of 1O2 increased from (0.324 ± 0.014) × 10−12 to (1.021 ± 0.040) × 10−12 mol L−1, as the initial concentrations of GEM were increased from 5 to 20 mg L−1. The second-order rate constant for the reaction of GEM with 1O2 was calculated to be 2.55 × 106 M−1 s−1. The primary transformation products were identified using HPLC-MS/MS, and possible photodegradation pathways were proposed by hydroxylation, aldehydes reactions, as well as the cleavage of ether side chains. The toxicity of phototransformation product evaluation revealed that photolysis potentially provides a critical pathway for GEM toxicity reduction in potable water and wastewater treatment facilities.

This is a preview of subscription content, log in to check access.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

References

  1. al Housari F, Vione D, Chiron S, Barbati S (2010) Reactive photoinduced species in estuarine waters. Characterization of hydroxyl radical, singlet oxygen and dissolved organic matter triplet state in natural oxidation processes. Photochem Photobiol Sci 9(1):78–86

  2. Andreozzi R, Raffaele M, Nicklas P (2003) Pharmaceuticals in STP effluents and their solar photodegradation in aquatic environment. Chemosphere 50(10):1319–1330

  3. Benotti MJ, Trenholm RA, Vanderford BJ, Holady JC, Stanford BD, Snyder SA (2008) Pharmaceuticals and endocrine disrupting compounds in US drinking water. Environ Sci Technol 43(3):597–603

  4. Boreen AL, Arnold WA, McNeill K (2003) Photodegradation of pharmaceuticals in the aquatic environment: a review. Aquat Sci 65(4):320–341

  5. Boreen AL, Arnold WA, McNeill K (2005) Triplet-sensitized photodegradation of sulfa drugs containing six-membered heterocyclic groups: identification of an SO2 extrusion photoproduct. Environ Sci Technol 39(10):3630–3638

  6. Boreen AL, Edhlund BL, Cotner JB, McNeill K (2008) Indirect photodegradation of dissolved free amino acids: the contribution of singlet oxygen and the differential reactivity of DOM from various sources. Environ Sci Technol 42(15):5492–5498

  7. Buxton GV, Greenstock CL, Helman WP, Ross AB (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(2):513–886

  8. Cermola M, DellaGreca M, Iesce MR (2005) Phototransformation of fibrate drugs in aqueous media. Environ Chem Lett 3(1):43–47

  9. Chen P, Lv W, Chen Z, Ma J, Li R, Yao K, Liu G, Li F (2015) Phototransformation of mefenamic acid induced by nitrite ions in water: mechanism, toxicity, and degradation pathways. Environ Sci Pollut Res 22(16):12585–12596

  10. Daughton CG, Ternes TA (1999) Pharmaceuticals and personal care products in the environment: agents of subtle change. Environ Health Perspect 107(Suppl 6):907

  11. Daughton CH, Ternes TA (2000) Special report: pharmaceuticals and personal care products in the environment: agents of subtle change? (vol 107, pg 907, 1999). Environ Health Perspect 108:598–598

  12. Doll TE, Frimmel FH (2003) Fate of pharmaceuticals-photodegradation by simulated solar UV-light. Chemosphere 52(10):1757–1769

  13. Evgenidou EN, Konstantinou IK, Lambropoulou DA (2015) Occurrence and removal of transformation products of PPCPs and illicit drugs in wastewaters: a review. Sci Total Environ 505:905–926

  14. Fang Y, Karnjanapiboonwong A, Chase DA (2012) Occurrence, fate, and persistence of gemfibrozil in water and soil. Environ Toxicol Chem 31(3):550–555

  15. Ferguson PJ, Bernot MJ, Doll JC, Lauer TE (2013) Detection of pharmaceuticals and personal care products (PPCPs) in near-shore habitats of southern Lake Michigan. Sci Total Environ 458:187–196

  16. Ge L, Chen J, Qiao X, Lin J, Cai X (2009) Light-source-dependent effects of main water constituents on photodegradation of phenicol antibiotics: mechanism and kinetics. Environ Sci Technol 43(9):3101–3107

  17. Ghorai TK, Chakraborty M, Pramanik P (2011) Photocatalytic performance of nanophotocatalyst from TiO2 and Fe2O3 by mechanochemical synthesis. J Alloys Compd 509(32):8158–8164

  18. Haag WR, Hoigne J (1986) Singlet oxygen in surface waters. 3. Photochemical formation and steady-state concentrations in various types of waters. Environ Sci Technol 20(4):341–348

  19. Hapeshi E, Achilleos A, Vasquez MI, Michael C, Xekoukoulotakis NP, Mantzavinos D, Kassinos D (2010) Drugs degrading photocatalytically: kinetics and mechanisms of ofloxacin and atenolol removal on titania suspensions. Water Res 44(6):1737–1746

  20. Hassan HB, Kata M, Erős I, Aigner Z (2004) Preparation and investigation of inclusion complexes containing gemfibrozil and DIMEB. J Incl Phenom Macrocycl Chem 50(3-4):219–225

  21. Heberer T (2002) Tracking persistent pharmaceutical residues from municipal sewage to drinking water. J Hydrol 266(3):175–189

  22. Homem V, Santos L (2011) Degradation and removal methods of antibiotics from aqueous matrices–a review. J Environ Manag 92(10):2304–2347

  23. Isidori M, Lavorgna M, Nardelli A, Parrella A, Previtera L, Rubino M (2005) Ecotoxicity of naproxen and its phototransformation products. Sci Total Environ 348(1):93–101

  24. Ji Y, Zeng C, Ferronato C, Chovelon JM, Yang X (2012) Nitrate-induced photodegradation of atenolol in aqueous solution: kinetics, toxicity and degradation pathways. Chemosphere 88(5):644–649

  25. Kosma CI, Lambropoulou DA, Albanis TA (2014) Investigation of PPCPs in wastewater treatment plants in Greece: occurrence, removal and environmental risk assessment. Sci Total Environ 466:421–438

  26. Kümmerer K (2000) The presence of pharmaceuticals in the environment due to human use-present knowledge and future challenges. J Environ Manag 90(8):2354–2366

  27. Kümmerer K (2001) Drugs in the environment: emission of drugs, diagnostic aids and disinfectants into wastewater by hospitals in relation to other sources–a review. Chemosphere 45(6):957–969

  28. Lishman L, Smyth SA, Sarafin K (2006) Occurrence and reductions of pharmaceuticals and personal care products and estrogens by municipal wastewater treatment plants in Ontario, Canada. Sci Total Environ 367(2):544–558

  29. Ma D, Liu G, Lv W, Yao K, Zhang X, Xiao H (2014) Photodegradation of naproxen in water under simulated solar radiation: mechanism, kinetics, and toxicity variation. Environ Sci Pollut Res 21(13):7797–7804

  30. Marco-Urrea E, Pérez-Trujillo M, Cruz-Morató C, Caminal G, Vicent T (2010) Degradation of the drug sodium diclofenac by Trametes versicolor pellets and identification of some intermediates by NMR. J Hazard Mater 176(1):836–842

  31. Mateus MCDA, Da Silva AM, Burrows HD (2000) Kinetics of photodegradation of the fungicide fenarimol in natural waters and in various salt solutions: salinity effects and mechanistic considerations. Water Res 34(4):1119–1126

  32. Miolo G, Viola G, Vedaldi D, Dall’Acqua F, Fravolini A, Tabarrini O, Cecchetti V (2002) In vitro phototoxic properties of new 6-desfluoro and 6-fluoro-8-methylquinolones. Toxicol in Vitro 16(6):683–693

  33. Ort C, Lawrence MG, Reungoat J, Mueller JF (2010) Sampling for PPCPs in wastewater systems: comparison of different sampling modes and optimization strategies. Environ Sci Technol 44(16):6289–6296

  34. Radjenovi J, Petrovic M, Barcelo D (2008) 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(3):831–841

  35. Rajabi HR, Farsi M (2015a) Effect of transition metal ion doping on the photocatalytic activity of ZnS quantum dots: synthesis, characterization, and application for dye decolorization. J Mol Catal A Chem 399:53–61

  36. Rajabi HR, Farsi M (2015b) Quantum dot based photocatalytic decolorization as an efficient and green strategy for the removal of anionic dye. Mater Sci Semicond Process 31:478–486

  37. Rajabi HR, Khani O, Shamsipur M (2013) High-performance pure and Fe3+-ion doped ZnS quantum dots as green nanophotocatalysts for the removal of malachite green under UV-light irradiation. J Hazard Mater 250:370–378

  38. Razavi B, Song W, Cooper WJ, Greaves J, Jeong J (2009) Free-radical-induced oxidative and reductive degradation of fibrate pharmaceuticals: kinetic studies and degradation mechanisms. J Phys Chem A 113(7):1287–1294

  39. Skolness SY, Durhan EJ, Jensen KM, Kahl MD, Makynen EA, Villeneuve DL, Ankley GT (2012) Effects of gemfibrozil on lipid metabolism, steroidogenesis, and reproduction in the fathead minnow (Pimephales promelas). Environ Toxicol Chem 31(11):2615–2624

  40. Spencer CM, Barradell LB (1996) Gemfibrozil-A reappraisal of its pharmacological properties and place in the management of dyslipidaemia. Drugs 51:982–1018

  41. 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(1):135–141

  42. Ternes TA, Meisenheimer M, McDowell D (2002) Removal of pharmaceuticals during drinking water treatment. Environ Sci Technol 36(17):3855–3863

  43. Urano Y, Higuchi T, Hirobe M (1996) Substrate-dependent changes of the oxidative O-dealkylation mechanism of several chemical and biological oxidizing systems. J Chem Soc Perkin Trans 2(6):1169–1173

  44. Westerhoff P, Yoon Y, Snyder S, Wert E (2005) Fate of endocrine-disruptor, pharmaceutical, and personal care product chemicals during simulated drinking water treatment processes. Environ Sci Technol 39(17):6649–6663

  45. Xu H, Cooper WJ, Jung J, Song W (2011) Photosensitized degradation of amoxicillin in natural organic matter isolate solutions. Water Res 45(2):632–638

  46. Yu Y, Wu L (2012) Analysis of endocrine disrupting compounds, pharmaceuticals and personal care products in sewage sludge by gas chromatography-mass spectrometry. Talanta 89:258–263

  47. Yurdakal S, Loddo V, Augugliaro V, Berber H, Palmisano G, Palmisano L (2007) Photodegradation of pharmaceutical drugs in aqueous TiO2 suspensions: mechanism and kinetics. Catal Today 129(1):9–15

  48. Zhan M, Yang X, Xian Q, Kong L (2006) Photosensitized degradation of bisphenol A involving reactive oxygen species in the presence of humic substances. Chemosphere 63(3):378–386

  49. Zhang N, Liu G, Liu H, Wang Y, He Z, Wang G (2011) Diclofenac photodegradation under simulated sunlight: effect of different forms of nitrogen and kinetic. J Hazard Mater 192(1):411–418

  50. Zhao JL, Ying GG, Liu YS (2010) Occurrence and a screening-level risk assessment of human pharmaceuticals in the Pearl River system, South China. Environ Toxicol Chem 29(6):1377–1384

  51. Zurita JL, Repetto G, Jos Á, Salguero M, López-Artíguez M, Cameán AM (2007) Toxicological effects of the lipid regulator gemfibrozil in four aquatic systems. Aquat Toxicol 81(1):106–115

Download references

Acknowledgments

This work is supported by the National Natural Science Foundation of China (No. 21377031) and the Scientific and Technical Projects of Guangdong Province (No. 2013B020800009). The authors would like to thank the anonymous reviewers and editors for their help in the improvement of this paper.

Author information

Correspondence to Wenying Lv.

Additional information

Highlights

• Photofate of gemfibrozil was studied under UV irradiation.

• The self-sensitized process via 1O2 had an apparent inhibitory effect on the degradation of GEM.

• Four photoproducts were determined by HPLC-MS/MS.

• Degradation pathways were proposed with three reactions.

• Toxicity of the phototransformation products was evaluated using Microtox test.

Responsible editor: Roland Kallenborn

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Ma, J., Lv, W., Chen, P. et al. Photodegradation of gemfibrozil in aqueous solution under UV irradiation: kinetics, mechanism, toxicity, and degradation pathways. Environ Sci Pollut Res 23, 14294–14306 (2016). https://doi.org/10.1007/s11356-016-6451-5

Download citation

Keywords

  • Gemfibrozil
  • Kinetics
  • Mechanism
  • Toxicity
  • Photodegradation pathways
  • UV irradiation