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Photodegradation of 17α-ethynylestradiol in nitrate aqueous solutions

  • Ren, Dong ;
  • Bi, Tingting ;
  • Gao, Shumei ;
  • Li, Xukun ;
  • Huang, Bin ;
  • Pan, Xuejun
  • Received : 2016.01.14
  • Accepted : 2016.03.01
  • Published : 2016.06.30

Abstract

$17{\alpha}$-Ethynylestradiol (EE2) has gotten growing concerns due to its widely detected in the environment and high estrogenic potency. However, the knowledge on the photochemical behaviors of EE2 in natural waters is still limited. Herein, the photodegradation and estrogenic potency variation of EE2 induced by nitrate were studied using a sunlight simulator consisted by a 300 W medium pressure mercury lamp and 290 nm cut-off filters. It was found that EE2 could be photodegraded at a rate of $0.0193h^{-1}$ in pure aqueous solutions, and the photodegradation of EE2 could be significantly promoted by nitrate. The photodegradation removal rate of EE2 was increased from 9% in Milli-Q water to 85% in 2.0 mM nitrate solutions. Reactive species scavenging experiments demonstrated that the photogenerated $HO{\bullet}$ contributed about 55% to EE2 degradation. Fe(III), Cl- and dissolved humic acid (DHA) could inhibit the photodegradation of EE2 by competing the incident light and photogenerated $HO{\bullet}$, while $HCO_3{^-}$ had no influence on EE2 photodegradation. EE2 was determined to be phototransformed into organic chemicals without estrogenic potency by GC-MS and MCF-7 cell proliferation toxicity tests. These findings could extend our knowledge on the photochemical behaviors of steroid estrogens and provide information for ecological risk assessment.

Keywords

Ecotoxicity;Nitrate ion;Reactive oxygen species;Photochemical behavior;$17{\alpha}$-Ethynylestradiol

References

  1. Rao K, Lei B, Li N, Ma M, Wang Z. Determination of estrogens and estrogenic activities in water from three rivers in Tianjin, China. J. Environ. Sci. 2013;25:1164-1171. https://doi.org/10.1016/S1001-0742(12)60149-1
  2. Liu R, Nelson DO, Hurley S, Hertz A, Reynolds P. Residential Exposure to Estrogen Disrupting Hazardous Air Pollutants and Breast Cancer Risk: The California Teachers Study. Epidemiol. 2015;26:365-373. https://doi.org/10.1097/EDE.0000000000000277
  3. Wolff SE, Veldhoen N, Helbing CC, Ramirez CA, Malpas JM, Propper CR. Estrogenic environmental contaminants alter the mRNA abundance profiles of genes involved in gonadal differ-entiation of the American bullfrog. Sci. Total Environ. 2015;521:380-387.
  4. Huang B, Wang B, Ren D, Jin W, Liu JL, Peng JH, Pan XJ. Occurrence, removal and bioaccumulation of steroid estrogens in Dianchi Lake catchment, China. Environ. Int. 2013;59:262-273. https://doi.org/10.1016/j.envint.2013.06.018
  5. Ayanda OS. Occurrence, analysis, toxicity and treatment processes of pharmaceutically active compounds and hormones in water and wastewater: A review. Int. J. Environ. Sci. 2015;6:56-67.
  6. Lee DG. Removal of a synthetic broad-spectrum antimicrobial agent, triclosan, in wastewater treatment systems: A short review. Environ. Eng. Res. 2015;20:111-120. https://doi.org/10.4491/eer.2014.081
  7. Sumpter JP, Johnson AC. 10th Anniversary perspective: reflections on endocrine disruption in the aquatic environment: from known knowns to unknown unknowns (and many things in between). J. Environ. Monit. 2008;10:1476-1485. https://doi.org/10.1039/b815741n
  8. Mazellier P, Meite L, De Laat J. Photodegradation of the steroid hormones $17{\beta}$-estradiol (E2) and $17{\alpha}$-ethinylestradiol (EE2) in dilute aqueous solution. Chemosphere. 2008;73:1216-1223. https://doi.org/10.1016/j.chemosphere.2008.07.046
  9. Liu X, Wu F, Deng N. Photodegradation of $17{\alpha}$-ethynylestradiol in aqueous solution exposed to a high-pressure mercury lamp (250 W). Environ. Pollut. 2003;126:393-398. https://doi.org/10.1016/S0269-7491(03)00229-X
  10. Jurgens MD, Holthaus KI, Johnson AC, Smith JJ, Hetheridge M, Williams RJ. The potential for estradiol and ethinylestradiol degradation in English rivers. Environ. Toxicol. Chem. 2002;21:480-488. https://doi.org/10.1002/etc.5620210302
  11. Zuo Y, Zhang K, Zhou S. Determination of estrogenic steroids and microbial and photochemical degradation of $17{\alpha}$ethinylestradiol (EE2) in lake surface water, a case study. Environ. Sci. Proc. Imp. 2013;15:1529-1535. https://doi.org/10.1039/c3em00239j
  12. Sarmah AK, Northcott GL, Scherr FF. Retention of estrogenic steroid hormones by selected New Zealand soils. Environ. Int. 2008;34:749-755. https://doi.org/10.1016/j.envint.2007.12.017
  13. Ying GG, Kookana RS, Dillon P. Sorption and degradation of selected five endocrine disrupting chemicals in aquifer material. Water Res. 2003;37:3785-3791. https://doi.org/10.1016/S0043-1354(03)00261-6
  14. Gupta VK, Jain R, Mittal A, Saleh TA, Nayak A, Agarwal S, Sikarwar S. Photo-catalytic degradation of toxic dye amaranth on TiO2/UV in aqueous suspensions. Mater. Sci. Eng., C. 2012;32:12-17. https://doi.org/10.1016/j.msec.2011.08.018
  15. Gupta VK, Jain R, Nayak A, Agarwal S, Shrivastava M. Removal of the hazardous dye-tartrazine by photodegradation on titanium dioxide surface. Mater. Sci. Eng., C. 2011;31:1062-1067. https://doi.org/10.1016/j.msec.2011.03.006
  16. Liu G, Liu H, Zhang N, Wang Y. Photodegradation of salicylic acid in aquatic environment: Effect of different forms of nitrogen. Sci. Total Environ. 2012;435:573-577.
  17. Saleh TA, Gupta VK. Photo-catalyzed degradation of hazardous dye methyl orange by use of a composite catalyst consisting of multi-walled carbon nanotubes and titanium dioxide. J. Colloid Interface Sci. 2012;371:101-106. https://doi.org/10.1016/j.jcis.2011.12.038
  18. Brezonik PL, Fulkerson-Brekken J. Nitrate-induced photolysis in natural waters: controls on concentrations of hydroxyl radical photo-intermediates by natural scavenging agents. Environ. Sci. Technol. 1998;32:3004-3010. https://doi.org/10.1021/es9802908
  19. Sharpless CM, Seibold DA, Linden KG. Nitrate photosensitized degradation of atrazine during UV water treatment. Aquat. Sci. 2003;65:359-366. https://doi.org/10.1007/s00027-003-0674-5
  20. Schlicker O, Ebert M, Fruth M, Weidner M, Wüst W, Dahmke A. Degradation of TCE with iron: the role of competing chromate and nitrate reduction. Groundwater 2000;38:403-409. https://doi.org/10.1111/j.1745-6584.2000.tb00226.x
  21. Ji Y, Zeng C, Ferronato C, Chovelon JM, Yang X. Nitrate-induced photodegradation of atenolol in aqueous solution: kinetics, tox-icity and degradation pathways. Chemosphere 2012;88:644-649. https://doi.org/10.1016/j.chemosphere.2012.03.050
  22. Mack J, Bolton JR. Photochemistry of nitrite and nitrate in aqueous solution: a review. J. Photochem. Photobiol. A. 1999;28:1-13.
  23. Ren D, Huang B, Bi TT, Xiong D, Pan XJ. Effects of pH and dissolved oxygen on the photodegradation of $17{\alpha}$-ethynylestradiol in dissolved humic acid solution. Environ. Sci. Proc. Imp. 2016;18:78-86. https://doi.org/10.1039/C5EM00502G
  24. Jamal JA, Ramli N, Stanslas J, Husian K. Estrogenic activity of selected Myrsinaceae species in MCF-7 human breast cancer cells. Int. J. Pharm. Pharm. Sci. 2012;4:547-553.
  25. Buxton GV, Greenstock CL, Helman WP, Ross AB. Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (${\cdot}OH/{\cdot}O^-$) in aqueous solution. J. Phys. Chem. Ref. Data. 1988;17:513-886. https://doi.org/10.1063/1.555805
  26. Whidbey CM, Daumit KE, Nguyen TH, Ashworth DD, Davis JC, Latch DE. Photochemical induced changes of in vitro estrogenic activity of steroid hormones. Water Res. 2012;46:5287-5296. https://doi.org/10.1016/j.watres.2012.07.016
  27. Lin AYC, Reinhard M. Photodegradation of common environmental pharmaceuticals and estrogens in river water. Environ. Toxicol. Chem. 2005;24:1303-1309. https://doi.org/10.1897/04-236R.1
  28. Matamoros V, Duhec A, Albaiges J, Bayona JM. Photodegradation of carbamazepine, ibuprofen, ketoprofen and $17{\alpha}$-ethinylestradiol in fresh and seawater. Water Air Soil Pollut. 2009;196:161-168. https://doi.org/10.1007/s11270-008-9765-1
  29. Chen Y, Zhang K, Zuo Y. Direct and indirect photodegradation of estriol in the presence of humic acid, nitrate and iron com-plexes in water solutions. Sci. Total Environ. 2013;463:802-809.
  30. Zhan M, Yang X, Xian Q, Kong L. Photochemical transformation of bisphenol A promoted by nitrate ions. Bull. Environ. Contam. Toxicol. 2006;76:105-112. https://doi.org/10.1007/s00128-005-0895-5
  31. Chiron S, Minero C, Vione D. Photodegradation processes of the antiepileptic drug carbamazepine, relevant to estuarine waters. Environ. Sci. Technol. 2006;40:5977-5983. https://doi.org/10.1021/es060502y
  32. Bouillon RC, Miller WL. Photodegradation of dimethyl sulfide (DMS) in natural waters: Laboratory assessment of the nitrate- photolysis-induced DMS oxidation. Environ. Sci. Technol. 2005;39:9471-9477. https://doi.org/10.1021/es048022z
  33. Song W, Yan S, Cooper WJ, Dionysiou DD, O'Shea KE. Hydroxyl radical oxidation of cylindrospermopsin (cyanobacterial toxin) and its role in the photochemical transformation. Environ. Sci. Technol. 2012;46:12608-12615. https://doi.org/10.1021/es302458h
  34. al Housari F, Vione D, Chiron S, Barbati S. Reactive photo-induced species in estuarine waters. Characterization of hydroxyl radical, singlet oxygen and dissolved organic matter triplet state in natural oxidation processes. Photochem. Photobiol. Sci. 2010;9:78-86. https://doi.org/10.1039/B9PP00030E
  35. Wenk J, Von Gunten U, Canonica S. Effect of dissolved organic matter on the transformation of contaminants induced by excited triplet states and the hydroxyl radical. Environ. Sci. Technol. 2011;45:1334-1340. https://doi.org/10.1021/es102212t
  36. Grebel JE, Pignatello JJ, Mitch WA. Impact of halide ions on natural organic matter-sensitized photolysis of $17{\beta}$-estradiol in saline waters. Environ. Sci. Technol. 2012;46:7128-7134. https://doi.org/10.1021/es3013613
  37. Lee C. Oxidation of organic contaminants in water by ironinduced oxygen activation: A short review. Environ. Eng. Res. 2015;20:205-211. https://doi.org/10.4491/eer.2015.051
  38. Wenk J, Canonica S. Phenolic antioxidants inhibit the triplet-induced transformation of anilines and sulfonamide antibiotics in aqueous solution. Environ. Sci. Technol. 2012;46:5455-5462. https://doi.org/10.1021/es300485u
  39. Feng W, Nansheng D. Photochemistry of hydrolytic iron (III) species and photoinduced degradation of organic compounds. A minireview. Chemosphere 2000;41:1137-1147. https://doi.org/10.1016/S0045-6535(00)00024-2
  40. Walse SS, Morgan SL, Kong L, Ferry JL. Role of dissolved organic matter, nitrate, and bicarbonate in the photolysis of aqueous fipronil. Environ. Sci. Technol. 2004;38:3908-3915. https://doi.org/10.1021/es0349047
  41. Espinoza LAT, Neamţu M, Frimmel FH. The effect of nitrate, Fe (III) and bicarbonate on the degradation of bisphenol A by simulated solar UV-irradiation. Water Res. 2007;41:4479-4487. https://doi.org/10.1016/j.watres.2007.06.060
  42. Vione D, Khanra S, Man SC, Maddigapu PR, Das R, Arsene C, Olariu RI, Maurino V, Minero C. Inhibition vs. enhancement of the nitrate-induced phototransformation of organic substrates by the OH scavengers bicarbonate and carbonate. Water Res. 2009;43:4718-4728. https://doi.org/10.1016/j.watres.2009.07.032
  43. Shah NS, Khan JA, Nawaz S, Ismail M, Khan K, Khan HM. Kinetic and mechanism investigation on the gamma irradiation induced degradation of endosulfan sulfate. Chemosphere 2015;121:18-25. https://doi.org/10.1016/j.chemosphere.2014.10.046
  44. Melloni G, Modena G, Tonellato U. Relative reactivities of carbon-carbon double and triple bonds toward electrophiles. Acc. Chem. Res. 1981;14:227-233. https://doi.org/10.1021/ar00068a001
  45. Antoniou MG, Shoemaker JA, Cruz AAdl, Dionysiou DD. Unveiling new degradation intermediates/pathways from the photocatalytic degradation of microcystin-LR. Environ. Sci. Technol. 2008;42:8877-8883. https://doi.org/10.1021/es801637z

Acknowledgement

Supported by : National Natural Science Foundation of China, Education Department Science Research Foundation of Yunnan Province, China Postdoctoral Science Foundation