Abstract
17-α ethinylestradiol (EE2) is a primary synthesized estrogen that is extensively used in oral contraception and hormone alternative treatment. EE2 photodegradation by TiO2 under solar irradiation was studied. The impact of various factors was optimized in the photocatalytic degradation of EE2, including the amount of TiO2 dosages, pH, intensity of light, irradiation time, and temperature of the reaction. At optimal condition, in the presence of 2.5 g L−1 TiO2, 10 mg L−1 of EE2 (pH 9) was completely degraded after 60 min of solar light irradiation at 18 °C temperature. The photocatalytic degradation process was observed to obey a pseudo–first–order kinetic equation with a rate constant of 0.104 min−1. After complete degradation of EE2, CO2 was found as the final product which was validated by change of TOC and COD values. During the degradation of EE2, two known and three unknown intermediate substances were detected by GC-MS. Molecular orbital (MO) simulation was used to estimate the point charge distribution and frontier electron density at every atom on the EE2 in order to inspect the mechanism of degradation. On the basis of detected intermediates, a probable degradation mechanism was suggested. The results of this study emphasize the significance of photodegradation on the elimination of estrogenic effect, mostly revealed by the phenol portion of EE2.
Highlights
• The photocatalytic efficacy of TiO2 to degrade EE2 under solar light irradiation was studied.
• The mineralization of EE2 was evaluated by analyzing the change in COD and TOC values.
• During the degradation, intermediate products were identified, and the mechanism is proposed.
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References
Ahern JC, Fairchild R, Thomas JS et al (2015) Characterization of BiOX compounds as photocatalysts for the degradation of pharmaceuticals in water. Appl Catal B Environ 179:229–238. https://doi.org/10.1016/j.apcatb.2015.04.025
Almaguer MA, Cruz YR, da Fonseca FV (2021) Combination of advanced oxidation processes and microalgae aiming at recalcitrant wastewater treatment and algal biomass production: a review. Environ Process 8:483–509. https://doi.org/10.1007/s40710-020-00492-x
Alver A, Basturk E (2019) Removal of aspartame by catalytic ozonation with nano-TiO2 coated pumice. Desalin Water Treat 152:268–275. https://doi.org/10.5004/dwt.2019.24016
Basturk E, Işık M, Karatas M (2019) Removal of aniline (Methylene blue) and azo (reactive red 198) dyes by photocatalysis via nano TiO2. Desalin Water Treat 143:306–313. https://doi.org/10.5004/dwt.2019.23522
Basturk E, Işık M, Karataş M (2021) Usage of titanium nanomaterial for the decolorization of methylene blue and reactive red 198 dyes by sonocatalysis. Desalin Water Treat 224:389–394. https://doi.org/10.5004/dwt.2021.27171
Basturk E, Karatas M (2014) Advanced oxidation of reactive Blue 181 solution: a comparison between Fenton and Sono-Fenton process. Ultrason Sonochem 21:1881–1885. https://doi.org/10.1016/j.ultsonch.2014.03.026
Basturk E, Karatas M (2015) Decolorization of antraquinone dye reactive Blue 181 solution by UV/H2O2 process. J Photochem Photobiol A Chem 299:67–72. https://doi.org/10.1016/j.jphotochem.2014.11.003
Basturk E, Karatas M (2021a) Photocatalytic removal of endocrine disrupting compounds from aqueous solution by different size nano-TiO2 under artificial uva. Desalin Water Treat 224:322–330. https://doi.org/10.5004/dwt.2021.27148
Basturk E, Karatas M (2021b) Removal of pharmaceuticals by advanced treatment methods. J Environ Manage 300:113808. https://doi.org/10.1016/j.jenvman.2021.113808
Beri KYV, Barbosa DP, Zbair M et al (2021) Adsorption of Estradiol from aqueous solution by hydrothermally carbonized and steam activated palm kernel shells. Energy Nexus 1:100009. https://doi.org/10.1016/j.nexus.2021.100009
Bilici Z, Bouchareb R, Sacak T et al (2021) Recycling of TiO2-containing waste and utilization by photocatalytic degradation of a reactive dye solution. Water Sci Technol 83:1242–1249. https://doi.org/10.2166/wst.2020.606
Chen Y, Zhang Y, Luo L et al (2018) A novel templated synthesis of C/N-doped β-Bi2O3 nanosheets for synergistic rapid removal of 17α-ethynylestradiol by adsorption and photocatalytic degradation. Ceram Int 44:2178–2185. https://doi.org/10.1016/j.ceramint.2017.10.173
Chen Y, Zhang Y, Shi X et al (2022) Controllable synthesis of Bi2SiO5/Bi4Si3O12 heterostructure and it’s specific adsorption and photocatalytic performance. Solid State Sci 132:106986. https://doi.org/10.1016/j.solidstatesciences.2022.106986
Çifçi DI, Tunçal T, Pala A, Uslu O (2016) Determination of optimum extinction wavelength for Paracetamol removal through energy efficient thin film reactor. J Photochem Photobiol A Chem 322–323:102–109. https://doi.org/10.1016/j.jphotochem.2016.03.003
Coleman HM, Chiang K, Amal R (2005) Effects of Ag and Pt on photocatalytic degradation of endocrine disrupting chemicals in water. Chem Eng J 113:65–72. https://doi.org/10.1016/j.cej.2005.07.014
Costa LL, Prado AGS (2009) TiO2 nanotubes as recyclable catalyst for efficient photocatalytic degradation of indigo carmine dye. J Photochem Photobiol A Chem 201:45–49. https://doi.org/10.1016/j.jphotochem.2008.09.014
Damacena DHL, Trigueiro P, Monteiro VH et al (2023) Saponite-inspired materials as remediation technologies for water treatment: an overview. Environ Process 10:15. https://doi.org/10.1007/s40710-023-00630-1
De Liz MV, De Lima RM, Do Amaral B et al (2018) Suspended and immobilized TiO2 photocatalytic degradation of estrogens: potential for application in wastewater treatment processes. J Braz Chem Soc 29:380–389. https://doi.org/10.21577/0103-5053.20170151
Dekkouche S, Morales-Torres S, Ribeiro AR et al (2022) In situ growth and crystallization of TiO2 on polymeric membranes for the photocatalytic degradation of diclofenac and 17α-ethinylestradiol. Chem Eng J 427:131476. https://doi.org/10.1016/j.cej.2021.131476
Dharma HNC, Jaafar J, Widiastuti N et al (2022) A review of Titanium Dioxide (TiO2)-based photocatalyst for oilfield-produced water treatment. Membranes 12:345. https://doi.org/10.3390/membranes12030345
Dhawle R, Giannakopoulos S, Frontistis Z, Mantzavinos D (2023) Peroxymonosulfate enhanced photoelectrocatalytic degradation of 17α-ethinyl estradiol. Catal Today 413–415:114026. https://doi.org/10.1016/j.cattod.2023.02.003
Duan Q, Li X, Wu Z et al (2019) Adsorption of 17β-estradiol from aqueous solutions by a novel hierarchically nitrogen-doped porous carbon. J Colloid Interface Sci 533:700–708. https://doi.org/10.1016/j.jcis.2018.09.007
Escudeiro de Oliveira M, Barroso BL, de Almeida J et al (2020) Photoelectrocatalytic degradation of 17α-ethinylestradiol and estrone under UV and visible light using nanotubular oxide arrays grown on Ti-0.5wt%W. Environ Res 191:110044. https://doi.org/10.1016/j.envres.2020.110044
Fast SA, Gude VG, Truax DD et al (2017) A critical evaluation of advanced oxidation processes for emerging contaminants removal. Environ Process 4:283–302. https://doi.org/10.1007/s40710-017-0207-1
Fedailaine M, Bellal B, Berkani S et al (2016) Photo-electrochemical characterization of the spinel CuFe2O4: application to Ni2+ removal under solar light. Environ Process 3:387–396. https://doi.org/10.1007/s40710-016-0142-6
Ferreira TLB, Garcia LMP, Gurgel GHM et al (2018) Effects of MnO2/In2O3 thin films on photocatalytic degradation 17 alpha-ethynylestradiol and methylene blue in water. J Mater Sci Mater Electron 29:12278–12287. https://doi.org/10.1007/s10854-018-9341-4
Frontistis Z, Daskalaki VM, Hapeshi E et al (2012a) Photocatalytic (UV-A/TiO2) degradation of 17α- ethynylestradiol in environmental matrices: experimental studies and artificial neural network modeling. J Photochem Photobiol A Chem 240:33–41. https://doi.org/10.1016/j.jphotochem.2012.05.007
Frontistis Z, Drosou C, Tyrovola K et al (2012b) Experimental and modeling studies of the degradation of estrogen hormones in aqueous TiO2 suspensions under simulated solar radiation. Ind Eng Chem Res 51:16552–16563. https://doi.org/10.1021/ie300561b
Fujishima A, Rao TN, Tryk DA (2000) Titanium dioxide photocatalysis. J Photochem Photobiol C Photochem Rev 1:1–21. https://doi.org/10.1016/S1389-5567(00)00002-2
Garcia JC, Takashima K (2003) Photocatalytic degradation of imazaquin in an aqueous suspension of titanium dioxide. J Photochem Photobiol A Chem 155:215–222. https://doi.org/10.1016/S1010-6030(02)00370-2
Hartmann J, Beyer R, Harm S (2014) Effective removal of Estrogens from drinking water and wastewater by adsorption technology. Environ Process 1:87–94. https://doi.org/10.1007/s40710-014-0005-y
Islam JB, Furukawa M, Tateishi I et al (2020a) Photocatalytic degradation of a typical neonicotinoid insecticide: nitenpyrum by ZnO nanoparticles under solar irradiatio. Environ Sci Pollut Res 27:20446–20456. https://doi.org/10.1007/s11356-020-08424-w
Islam MR, Islam JB, Furukawa M et al (2020b) Photocatalytic degradation of a systemic herbicide: Picloram from aqueous solution using titanium oxide (TiO2) under sunlight. ChemEngineering 4:1–14. https://doi.org/10.3390/chemengineering4040058
Kosmulski M (2002) The significance of the difference in the point of zero charge between rutile and anatase. Adv Colloid Interface Sci 99:255–264. https://doi.org/10.1016/S0001-8686(02)00080-5
Kovacic M, Kopcic N, Kusic H, Bozic AL (2018) Solar driven degradation of 17β-estradiol using composite photocatalytic materials and artificial irradiation source: influence of process and water matrix parameters. J Photochem Photobiol A Chem 361:48–61. https://doi.org/10.1016/j.jphotochem.2018.05.015
Kralchevska R, Milanova M, Bistan M et al (2012) The photocatalytic degradation of 17α-ethynylestradiol by pure and carbon nanotubes modified TiO2 under UVC illumination. Cent Eur J Chem 10:1137–1148. https://doi.org/10.2478/s11532-012-0017-2
Li J, Chen C, Zhao J et al (2002) Photodegradation of dye pollutants on TiO2 nanoparticles dispersed in silicate under UV - VIS irradiation. Appl Catal B Environ 37:331–338. https://doi.org/10.1016/S0926-3373(02)00011-5
Li Puma G, Puddu V, Tsang HK et al (2010) Photocatalytic oxidation of multicomponent mixtures of estrogens (estrone (E1), 17β-estradiol (E2), 17α-ethynylestradiol (EE2) and estriol (E3)) under UVA and UVC radiation: photon absorption, quantum yields and rate constants Independent of photon absorp. Appl Catal B Environ 99:388–397. https://doi.org/10.1016/j.apcatb.2010.05.015
Li S, Sun W (2014) Photocatalytic degradation of 17α-ethinylestradiol in mono- and binary systems of fulvic acid and Fe(III): application of fluorescence excitation/emission matrixes. Chem Eng J 237:101–108. https://doi.org/10.1016/j.cej.2013.10.002
Lima KVL, Emídio ES, Pupo Nogueira RF et al (2020) Application of a stable Ag/TiO2 film in the simultaneous photodegradation of hormones. J Chem Technol Biotechnol 95:2656–2663. https://doi.org/10.1002/jctb.6258
Liu XL, Wu F, Deng NS (2003) Photodegradation of 17α-ethynylestradiol in aqueous solution exposed to a high-pressure mercury lamp (250 W). Environ Pollut 126:393–398. https://doi.org/10.1016/S0269-7491(03)00229-X
Luo L, Long J, Zhao S et al (2019a) Effective visible-light-driven photocatalytic degradation of 17Α-ethynylestradiol by crosslinked CdS nano-rod/TiO2 (B) nano-belt composite. Process Saf Environ Prot 130:77–85. https://doi.org/10.1016/j.psep.2019.08.001
Luo L, Xia L, Tan W et al (2019b) The TiO2 (B) nano-belts with excellent performance prepared via alkaline stirring hydrothermal method and its application to remove 17α-ethynylestradiol. Environ Sci Pollut Res 26:34018–34026. https://doi.org/10.1007/s11356-018-3122-8
Luo L, Meng D, He L et al (2022) Photocatalytic activation of peroxydisulfate by a new porous g-C3N4/reduced graphene oxide/TiO2 nanobelts composite for efficient degradation of 17α-ethinylestradiol. Chem Eng J 446:137325. https://doi.org/10.1016/j.cej.2022.137325
Majhi D, Kumar Mishra A, Das K et al (2021) Plasmonic Ag nanoparticle decorated Bi2O3/CuBi2O4 photocatalyst for expeditious degradation of 17α-ethinylestradiol and cr(VI) reduction: insight into electron transfer mechanism and enhanced photocatalytic activity. Chem Eng J 413:127506. https://doi.org/10.1016/j.cej.2020.127506
Martin MV, Eusebi AL, Manassero A et al (2023a) Degradation of binary mixtures of water pollutants in a photocatalytic microreactor: competitive kinetics with explicit radiation absorption effects. J Environ Chem Eng 11:110929. https://doi.org/10.1016/j.jece.2023.110929
Martin MV, Rossi L, Rosso JA et al (2023b) Palladium-modified TiO2 films in a photocatalytic microreactor: evaluation of radiation absorption properties and pollutant degradation efficiency. Photochem Photobiol Sci 22:47–58. https://doi.org/10.1007/s43630-022-00296-y
Matsuoka S, Kikuchi M, Kimura S et al (2005) Determination of estrogenic substances in the water of Muko River using in vitro assays, and the degradation of natural estrogens by aquatic bacteria. J Heal Sci 51:178–184. https://doi.org/10.1248/jhs.51.178
Menon NG, George L, Tatiparti SSV, Mukherji S (2021) Efficacy and reusability of mixed-phase TiO2–ZnO nanocomposites for the removal of estrogenic effects of 17β-Estradiol and 17α-Ethinylestradiol from water. J Environ Manage 288:112340. https://doi.org/10.1016/j.jenvman.2021.112340
Mirmasoomi SR, Mehdipour Ghazi M, Galedari M (2017) Photocatalytic degradation of diazinon under visible light using TiO2/Fe2O3 nanocomposite synthesized by ultrasonic-assisted impregnation method. Sep Purif Technol 175:418–427. https://doi.org/10.1016/j.seppur.2016.11.021
Molla MAI, Ahsan S, Tateishi I et al (2018a) Degradation, kinetics, and mineralization in solar photocatalytic treatment of aqueous amitrole solution with titanium dioxide. Environ Eng Sci 35:401–407. https://doi.org/10.1089/ees.2017.0138
Molla MAI, Furukawa M, Tateishi I et al (2018b) Solar photocatalytic decomposition of Probenazole in water with TiO2 in the presence of H2O2. Energy sources, part A recover. Util Environ Eff 40:2432–2441. https://doi.org/10.1080/15567036.2018.1502840
Molla MAI, Furukawa M, Tateishi I et al (2019) Optimization of Alachlor Photocatalytic degradation with Nano-TiO2 in water under solar illumination: reaction pathway and mineralization. Clean Technol 1:141–153. https://doi.org/10.3390/cleantechnol1010010
Molla MAI, Furukawa M, Tateishi I et al (2020) Mineralization of Diazinon with nanosized-photocatalyst TiO2 in water under sunlight irradiation: optimization of degradation conditions and reaction pathway. Environ Technol (United Kingdom) 41:3524–3533. https://doi.org/10.1080/09593330.2019.1615129
Nasikhudin DM, Kusumaatmaja A, Triyana K (2018) Study on Photocatalytic properties of TiO2 nanoparticle in various pH condition. J Phys Conf Ser 1011:012069. https://doi.org/10.1088/1742-6596/1011/1/012069
Ncube P, Zvinowanda C, Belaid M, Ntuli F (2023) Heterogeneous photocatalytic degradation of Nevirapine in wastewater using the UV/TiO2/H2O2 process. Environ Process 10:1. https://doi.org/10.1007/s40710-022-00615-6
Noutsopoulos C, Charalambous V, Koumaki E (2020) Evaluating the fate of emerging contaminants in wastewater treatment plants through plant-wide mathematical modelling. Environ Process 7:1065–1094. https://doi.org/10.1007/s40710-020-00459-y
Pan Z, Stemmler EA, Cho HJ et al (2014) Photocatalytic degradation of 17α-ethinylestradiol (EE2) in the presence of TiO2-doped zeolite. J Hazard Mater 279:17–25. https://doi.org/10.1016/j.jhazmat.2014.06.040
Pi X, Zhang S, Wang L et al (2021) BiVO4 photo-catalyst with controllable wettability and its improved visible light catalytic activity for degradation of 17α-Ethinylestradiol. J Taiwan Inst Chem Eng 127:140–150. https://doi.org/10.1016/j.jtice.2021.07.040
Prokić D, Vukčević M, Kalijadis A et al (2020) Removal of Estrone, 17β-Estradiol, and 17α-Ethinylestradiol from water by adsorption onto chemically modified activated Carbon Cloths. Fibers Polym 21:2263–2274. https://doi.org/10.1007/s12221-020-9758-2
Rashki O, Rezaei MR, Sayadi MH (2022) The high photocatalytic efficiency and stability of the Z-scheme CaTiO3/WS2 heterostructure for photocatalytic removal of 17α-ethinyl estradiol in aqueous solution. J Photochem Photobiol A Chem 433:114169. https://doi.org/10.1016/j.jphotochem.2022.114169
Reis R, Dhawle R, Du Pasquier D et al (2023) Electrochemical degradation of 17α-ethinylestradiol: transformation products, degradation pathways and in vivo assessment of estrogenic activity. Environ Int 176:107992. https://doi.org/10.1016/j.envint.2023.107992
Rezende TTA, Garcia LMP, Ferreira TLB et al (2020) Removal study of the hormone17 alpha-ethynylestradiol and methylene blue dye from water using TiO2, Mn2O3 and TiO2/Mn2O3 thin films. J Mater Sci Mater Electron 31:9260–9269. https://doi.org/10.1007/s10854-020-03466-9
Sedighi M, Nasseri S, Ghotbi-Ravandi AA (2019) Degradation of 17α-ethinylestradiol by Enterobacter Tabaci isolate and kinetic characterization. Environ Process 6:741–755. https://doi.org/10.1007/s40710-019-00377-8
Shi M, Luo L, Dai J et al (2020) The comparative study of two kinds of β-Bi2O3/TiO2 binary composite and their removal of 17ɑ-ethynylestradiol. Environ Sci Pollut Res 27:24692–24701. https://doi.org/10.1007/s11356-019-06348-8
Shi Y, Luo L, Zhang Y et al (2018) Synthesis and characterization of porous platelet-shaped α-Bi2O3 with enhanced photocatalytic activity for 17α-ethynylestradiol. J Mater Sci 53:1049–1064. https://doi.org/10.1007/s10853-017-1553-0
Šojić Merkulov D, Vlazan P, Poienar M et al (2022) Sustainable removal of 17α-ethynylestradiol from aqueous environment using rare earth doped lanthanum manganite nanomaterials. Catal Today 424:113746. https://doi.org/10.1016/j.cattod.2022.05.011
Song J, Shi M, Xia L et al (2023) The comparative study on inhibitory effect of natural organic matters on the TiO2 and activated carbon/TiO2 composites for the removal of 17α-ethinylestradiol. Chemosphere 333:138930. https://doi.org/10.1016/j.chemosphere.2023.138930
Sun W, Li S, Mai J, Ni J (2010) Initial photocatalytic degradation intermediates/pathways of 17α-ethynylestradiol: effect of pH and methanol. Chemosphere 81:92–99. https://doi.org/10.1016/j.chemosphere.2010.06.051
Vaddadi LP, Avisar D, Vadivel VK et al (2020) LP-UV-Nano MgO2 pretreated catalysis followed by small bioreactor platform capsules treatment for superior kinetic degradation performance of 17α-Ethynylestradiol. Materials 13:83. https://doi.org/10.3390/ma13010083
Vinod Kumar V et al (2020) Rapid visible-light degradation of EE2 and its estrogenicity in hospital wastewater by crystalline promoted g-C3N4. J Hazard Mater 398:122880. https://doi.org/10.1016/j.jhazmat.2020.122880
Wang D, Li Y, Li G et al (2013) Modeling of quantitative effects of water components on the photocatalytic degradation of 17α-ethynylestradiol in a modified flat plate serpentine reactor. J Hazard Mater 254–255:64–71. https://doi.org/10.1016/j.jhazmat.2013.03.049
Wang Y, Li Y, Zhang W et al (2015) Photocatalytic degradation and reactor modeling of 17α-ethynylestradiol employing titanium dioxide-incorporated foam concrete. Environ Sci Pollut Res 22:3508–3517. https://doi.org/10.1007/s11356-014-3573-5
Zhang C, Li Y, Wang D et al (2015) Ag@helical chiral TiO2 nanofibers for visible light photocatalytic degradation of 17α-ethinylestradiol. Environ Sci Pollut Res 22:10444–10451. https://doi.org/10.1007/s11356-015-4251-y
Zuo Y, Xia L, Luo L et al (2023) 17α-Ethinylestradiol abatement by O-doped porous carbon nitride in the presence of peroxydisulfate. React Kinet Mech Catal 136:1423–1435. https://doi.org/10.1007/s11144-023-02421-z
Zuo Y, Zhang K, Zhou S (2013) Determination of estrogenic steroids and microbial and photochemical degradation of 17α-ethinylestradiol (EE2) in lake surface water, a case study. Environ Sci Process Impacts 15:1529–1535. https://doi.org/10.1039/c3em00239j
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The present research was partly supported by Grant-in-Aid for Scientific Research (B) 21H03642 from the Ministry of Education, Culture, Sports, Science, and Technology of Japan.
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A.K.: Conceptualization, writing-original draft, and writing-review and editing. M.F.: formal analysis, data curation and writing-review and editing. I. T.: formal analysis, and writing-review and editing. H.K.: writing-review and editing. M.H.S.: conceptualization and writing-review and editing. J.B.I.: writing-review and editing. S.K.: writing-review and editing and supervision.
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Khatun, A., Furukawa, M., Tateishi, I. et al. Photocatalytic Degradation of Endocrine Disrupting Chemical 17-α Ethinylestradiol by TiO2 Nanoparticles Under Solar Light Irradiation. Environ. Process. 11, 1 (2024). https://doi.org/10.1007/s40710-023-00678-z
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DOI: https://doi.org/10.1007/s40710-023-00678-z