Applied Chemical Engineering

Photocatalytic oxidation of psychoactive drug Duloxetine: Degradation kinetics, inorganic ions and phytotoxicity evaluation

Sophia Tsoumachidou

Laboratory of Physical Chemistry, Department of Chemistry, Aristotle University of Thessaloniki

Maria Valari

InterBalkan Environment Center

Ioannis Poulios

Laboratory of Physical Chemistry, Department of Chemistry, Aristotle University of Thessaloniki

DOI: https://doi.org/10.24294/ace.v3i1.509

Keywords: Duloxetine, Photocatalytic Oxidation, Psychoactive Drug, Urban Wastewater

---

Abstract

Pharmaceutically active compounds, emerging extensively in ecosystems as pollutants, have become an important environmental and public health issue, since they can contaminate drinking water and pose threat to wildlife and human health. Therefore, efforts should be made in order to establish proper methods for their inactivation or elimination in the environment. The photocatalytic oxidation of psychoactive drug Duloxetine (DLX) has been investigated. In the case of heterogeneous photocatalytic oxidation, the effect of TiO₂ P25 concentration (0.1–1 g L^-1), initial concentration of H₂O₂ (0.25–0.2 g L^-1) and Fe³⁺ (0.00175–0.014 g L^-1) and pH of the solution (3–10) on initial reaction rates were evaluated, while for homogeneous photocatalytic oxidation the effect of the amount of H₂O₂ (0.25–0.2 g L^-1) and Fe³⁺ (0.00175–0.014 g L^-1) were investigated. Additionally, the conversion of the heteroatoms in the molecule of DLX to inorganic ions (NO₃^-, NH₄⁺, SO₄^2-) during photocatalytic process has been observed, and phytotoxicity testing, using three plant species, was carried out in order to examine the effect of photocatalytic oxidation on the toxicity of DLX. According to the results presented in this study, both heterogeneous and homogeneous photocatalytic oxidation is an efficient methodology for DLX degradation.

---

References

[1] Hofman-Caris CHM, Siegers WG, Van de Merlen K, et al. Removal of pharmaceuticals from WWTP effluent: Removal of EFOM followed by advanced oxidation. Chemical Engineering Journal 2017; 327 (Supplement C): 514–521. doi: https://doi.org/10.1016/j.cej.2017.06.154.

[2] Pereira AMPT, Silva LJG, Laranjeiro CSM, et al. Human pharmaceuticals in Portuguese rivers: The impact of water scarcity in the environmental risk. Science of the Total Environment 2017; 609 (Supplement C): 1182–1191. doi: https://doi.org/10.1016/j.scitotenv.2017.07.200.

[3] Xekoukoulotakis NP, Xinidis N, Chroni M, et al. UV-A/TiO2 photocatalytic decomposition of erythromycin in water: Factors affecting mineralization and antibiotic activity. Catalysis Today 2010; 151(1): 29–33. doi: http://dx.doi.org/10.1016/j.cattod.2010.01.040.

[4] Ramirez AJ, Brain RA, Usenko S, et al. Occurrence of pharmaceuticals and personal care products in fish: Results of a national pilot study in the United States. Environmental Toxicology and Chemistry 2009; 28 (12): 2587–2597. doi: 10.1897/08-561.1.

[5] Bu Q, Shi X, Yu G, et al. Pay attention to non-wastewater emission pathways of pharmaceuticals into environments. Chemosphere 2016; 165 (Supplement C): 515–518. doi: https://doi.org/10.1016/j.chemosphere.2016.09.078.

[6] Puckowski A, Mioduszewska K, Łukaszewicz P, et al. Bioaccumulation and analytics of pharmaceutical residues in the environment: A review. Journal of Pharmaceutical and Biomedical Analysis 2016; 127 (Supplement C): 232–255. doi: https://doi.org/10.1016/j.jpba.2016.02.049.

[7] Menken M, Munsat TL, Toole JF. The global burden of disease study: Implications for neurology. Archives of Neurology 2000; 57(3): 418–420. doi: 10.1001/archneur.57.3.418.

[8] Almeida N, Mari JD, Coutinho E, et al. Brazilian multicentric study of psychiatric morbidity — Methodological features and prevalence estimates. British Journal of Psychiatry 1997; 171: 524–529. doi: 10.1192/bjp.171.6.524.

[9] Saraceno B. The WHO World Health Report 2001 on mental health. Epidemiologia e Psichiatria Sociale 2002; 11(2): 83–87. doi: 10.1017/s1121189x00005546.

[10] Brooks BW, Turner PK, Stanley JK, et al. Waterborne and sediment toxicity of fluoxetine to select organisms. Chemosphere 2003; 52(1): 135–142. doi: https://doi.org/10.1016/S0045-6535(03)00103-6.

[11] Van der Ven K, Keil D, Moens LN, et al. Effects of the antidepressant mianserin in zebrafish: Molecular markers of endocrine disruption. Chemosphere 2006; 65(10): 1836–1845. doi: https://doi.org/10.1016/j.chemosphere.2006.03.079.

[12] Escher BI, Bramaz N, Richter M, et al. Comparative ecotoxicological hazard assessment of beta-blockers and their human metabolites using a mode-of-action-based test battery and a QSAR approach. Environmental Science & Technology 2006; 40(23): 7402–7408. doi: 10.1021/es052572v.

[13] Rosi-Marshall EJ, Snow D, Bartelt-Hunt SL, et al. A review of ecological effects and environmental fate of illicit drugs in aquatic ecosystems. Journal of Hazardous Materials 2015; 282: 18–25. doi: https://doi.org/10.1016/j.jhazmat.2014.06.062.

[14] Thomas MA, Klaper RD. Psychoactive pharmaceuticals induce fish gene expression profiles associated with human idiopathic autism. PLoS ONE 2012; 7(6): e32917. doi: 10.1371/journal.pone.0032917.

[15] Thomaidis NS, Gago-Ferrero P, Ort C, et al. Reflection of socioeconomic changes in wastewater: Licit and illicit drug use patterns. Environmental Science & Technology 2016; 50(18): 10065–10072. doi: 10.1021/acs.est.6b02417.

[16] Rodayan A, Afana S, Segura PA, et al. Linking drugs of abuse in wastewater to contamination of surface and drinking water. Environmental Toxicology and Chemistry 2016; 35(4): 843–849. doi: 10.1002/etc.3085.

[17] Chu S, Metcalfe CD. Analysis of paroxetine, fluoxetine and norfluoxetine in fish tissues using pressurized liquid extraction, mixed mode solid phase extraction cleanup and liquid chromatography — tandem mass spectrometry. Journal of Chromatography A 2007; 1163(1): 112–118. doi: http://dx.doi.org/10.1016/j.chroma.2007.06.014.

[18] Tiedeken EJ, Tahar A, McHugh B, et al. Monitoring, sources, receptors, and control measures for three European Union watch list substances of emerging concern in receiving waters — A 20 year systematic review. Science of the Total Environment 2017; 574 (Supplement C): 1140–1163. doi: https://doi.org/10.1016/j.scitotenv.2016.09.084.

[19] Barbosa MO, Moreira NFF, Ribeiro AR, et al. Occurrence and removal of organic micropollutants: An overview of the watch list of EU Decision 2015/495. Water Research 2016; 94 (Supplement C): 257–279. doi: https://doi.org/10.1016/j.watres.2016.02.047.

[20] EU. European Union: Directive 2013/39/EU of the European Parliament and of the Council of 12 August 2013 amending Directives 2000/60/EC and 2008/105/EC as regards priority substances in the field of water policy. Official Journal of the European Union 2013; L226: 1–17.

[21] Kelessidis A, Stasinakis AS. Comparative study of the methods used for treatment and final disposal of sewage sludge in European countries. Waste Management 2012; 32(6): 1186–1195. doi: https://doi.org/10.1016/j.wasman.2012.01.012.

[22] Thakur M, Sharma G, Ahamad T, et al. Efficient photocatalytic degradation of toxic dyes from aqueous environment using gelatin-Zr(IV) phosphate nanocomposite and its antimicrobial activity. Colloids and Surfaces B: Biointerfaces 2017; 157 (Supplement C): 456–463. doi: https://doi.org/10.1016/j.colsurfb.2017.06.018.

[23] Bogatu C, Perniu D, Sau C, et al. Ultrasound assisted sol-gel TiO2 powders and thin films for photocatalytic removal of toxic pollutants. Ceramics International 2017; 43(11): 7963–7969. doi: https://doi.org/10.1016/j.ceramint.2017.03.054.

[24] Braun AM, Maurette MT, Oliveros E. Photochemical Technology. Chichester: John Wiley & Sons Wiley; 1991.

[25] Sriwichai S, Ranwongsa H, Wetchakun K, et al. Effect of iron loading on the photocatalytic performance of Bi2WO6 photocatalyst. Superlattices and Microstructures 2014; 76 (Supplement C): 362–375. doi: https://doi.org/10.1016/j.spmi.2014.10.014.

[26] Tsoumachidou S, Velegraki T, Antoniadis A, et al. Greywater as a sustainable water source: A photocatalytic treatment technology under artificial and solar illumination. Journal of Environmental Management 2017; 195: 232–241. doi: 10.1016/j.jenvman.2016.08.025.

[27] Tsoumachidou S, Velegraki T, Poulios I. TiO2 photocatalytic degradation of UV filter para-aminobenzoic acid under artificial and solar illumination. Journal of Chemical Technology and Biotechnology 2016; 91 (6): 1773–1781. doi: 10.1002/jctb.4768.

[28] Sakthivel S, Neppolian B, Shankar MV, et al. Solar photocatalytic degradation of azo dye: comparison of photocatalytic efficiency of ZnO and TiO2. Solar Energy Materials and Solar Cells 2003; 77(1): 65–82. doi: 10.1016/S0927-0248(02)00255-6.

[29] Babuponnusami A, Muthukumar K. A review on Fenton and improvements to the Fenton process for wastewater treatment. Journal of Environmental Chemical Engineering 2014; 2 (1): 557–572. doi: https://doi.org/10.1016/j.jece.2013.10.011.

[30] Gaya UI, Abdullah AH. Heterogeneous photocatalytic degradation of organic contaminants over titanium dioxide: A review of fundamentals, progress and problems. Journal of Photochemistry and Photobiology C: Photochemistry Reviews 2008; 9(1): 1–12. doi: https://doi.org/10.1016/j.jphotochemrev.2007.12.003.

[31] Liu T, Li X, Yuan X, et al. Enhanced visible-light photocatalytic activity of a TiO2 hydrosol assisted by H2O2: Surface complexation and kinetic modeling. Journal of Molecular Catalysis A: Chemical 2016; 414 (Supplement C): 122–129. doi: https://doi.org/10.1016/j.molcata.2016.01.011.

[32] Boroski M, Rodrigues AC, Garcia JC, et al. Combined electrocoagulation and TiO2 photoassisted treatment applied to wastewater effluents from pharmaceutical and cosmetic industries. Journal of Hazardous Materials 2009; 162(1): 448–454. doi: https://doi.org/10.1016/j.jhazmat.2008.05.062.

[33] Rajeshwar K, Osugi ME, Chanmanee W, et al. Heterogeneous photocatalytic treatment of organic dyes in air and aqueous media. Journal of Photochemistry and Photobiology C: Photochemistry Reviews 2008; 9(4): 171–192. doi: https://doi.org/10.1016/j.jphotochemrev.2008.09.001.

[34] Rincón AG, Pulgarin C. Absence of E. coli regrowth after Fe3+ and TiO2 solar photoassisted disinfection of water in CPC solar photoreactor. Catalysis Today 2007; 124(3): 204–214. doi: http://dx.doi.org/10.1016/j.cattod.2007.03.039.

[35] Nahar MS, Hasegawa K, Kagaya S, et al. Adsorption and aggregation of Fe(III)–hydroxy complexes during the photodegradation of phenol using the iron-added-TiO2 combined system. Journal of Hazardous Materials 2009; 162(1): 351–355. doi: http://dx.doi.org/10.1016/j.jhazmat.2008.05.046.

[36] Měánková H, Mailhot G, Jirkovský J, et al. Effect of iron speciation on the photodegradation of Monuron in combined photocatalytic systems with immobilized or suspended TiO2. Environmental Chemistry Letters 2009; 7(2): 127–132. doi: 10.1007/s10311-008-0145-2.

[37] Mir NA, Haque MM, Khan A, et al. Photocatalytic degradation of herbicide Bentazone in aqueous suspension of TiO2: Mineralization, identification of intermediates and reaction pathways. Environmental Technology 2014; 35(4): 407–415. doi: 10.1080/09593330.2013.829872.

[38] Lin Y, Ferronato C, Deng N, et al. Study of benzylparaben photocatalytic degradation by TiO2. Applied Catalysis B: Environmental 2011; 104(3): 353–360. doi: https://doi.org/10.1016/j.apcatb.2011.03.006.

[39] Helali S, Dappozze F, Horikoshi S, et al. Kinetics of the photocatalytic degradation of methylamine: Influence of pH and UV-A/UV-B radiant fluxes. Journal of Photochemistry and Photobiology A: Chemistry 2013; 255 (Supplement C): 50–57. doi: https://doi.org/10.1016/j.jphotochem.2012.12.022.

[40] Tizaoui C, Mezughi K, Bickley R. Heterogeneous photocatalytic removal of the herbicide clopyralid and its comparison with UV/H2O2 and ozone oxidation techniques. Desalination 2011; 273(1): 197–204. doi: https://doi.org/10.1016/j.desal.2010.11.036.

[41] Ahmed S, Rasul MG, Martens WN, et al. Heterogeneous photocatalytic degradation of phenols in wastewater: A review on current status and developments. Desalination 2010; 261(1-2): 3–18. doi: 10.1016/j.desal.2010.04.062.

[42] Datar PA, Waghmare RU. Development and validation of an analytical method for the stability of duloxetine hydrochloride. Journal of Taibah University for Science 2014; 8(4): 357–63. doi: https://doi.org/10.1016/j.jtusci.2014.06.001.

[43] Sinha VR, Kumria AR, Bhinge JR. Stress Degradation Studies on Duloxetine Hydrochloride and Development of an RP-HPLC Method for its Determination in Capsule Formulation. Journal of Chromatographic Science 2009; 47(7): 589–593.

[44] Carneiro PA, Nogueira RFP, Zanoni MVB. Homogeneous photodegradation of CI Reactive Blue 4 using a photo-Fenton process under artificial and solar irradiation. Dyes and Pigments 2007; 74(1): 127–132. doi: 10.1016/j.dyepig.2006.01.022.

[45] Baba Y, Yatagai T, Harada T, et al. Hydroxyl radical generation in the photo-Fenton process: Effects of carboxylic acids on iron redox cycling. Chemical Engineering Journal 2015; 277: 229–241. doi: 10.1016/j.cej.2015.04.103.

[46] Mirzaei A, Chen Z, Haghighat F, et al. Removal of pharmaceuticals from water by homo/heterogonous Fenton-type processes — A review. Chemosphere 2017; 174 (Supplement C): 665–688. doi: https://doi.org/10.1016/j.chemosphere.2017.02.019.

[47] Abdessalem AK, Bellakhal N, Oturan N, et al. Treatment of a mixture of three pesticides by photo- and electro-Fenton processes. Desalination 2010; 250 (1): 450–455. doi: 10.1016/j.desal.2009.09.072.

[48] Tsoumachidou S, Lambropoulou D, Poulios I. Homogeneous photocatalytic oxidation of UV filter para-aminobenzoic acid in aqueous solutions. Environmental Science and Pollution Research 2017; 24 (2): 1113–1121. doi: 10.1007/s11356-016-7434-2.

[49] Malato S, Fernandez-Ibanez P, Maldonado MI, et al. Decontamination and disinfection of water by solar photocatalysis: Recent overview and trends. Catalysis Today 2009; 147(1): 1–59. doi: 10.1016/j.cattod.2009.06.018.

[50] Xu X, Li X, Li X, et al. Degradation of melatonin by UV, UV/H2O2, Fe2+/H2O2 and UV/Fe2+/H2O2 processes. Separation and Purification Technology 2009; 68(2): 261–266. doi: 10.1016/j.seppur.2009.05.013.

[51] Ioannou LA, Fatta-Kassinos D. Solar photo-Fenton oxidation against the bioresistant fractions of winery wastewater. Journal of Environmental Chemical Enginneering 2013; (1): 703–712.

[52] Gernjak W, Krutzler T, Glaser A, et al. Photo-Fenton treatment of water containing naturalphenolic pollutants. Chemosphere 2003; 50(1): 71–78. doi: 10.1016/S0045-6535(02)00403-4.

[53] Yang M, Hu J, Ito K. Characteristics of Fe2+/H2O2/UV oxidization process. Environmental Technology 1998; 19(2): 183–191. doi: 10.1080/09593331908616670.

[54] Navarro S, Fenoll J, Vela N, et al. Removal of ten pesticides from leaching water at pilot plant scale by photo-Fenton treatment. Chemical Engineering Journal 2011; 167(1): 42–49. doi: 10.1016/j.cej.2010.11.105.

[55] Doumic LI, Soares PA, Ayude MA, et al. Enhancement of a solar photo-Fenton reaction by using ferrioxalate complexes for the treatment of a synthetic cotton-textile dyeing wastewater. Chemical Engineering Journal 2015; 277: 86–96. doi: 10.1016/j.cej.2015.04.074.

[56] Nohara K, Hidaka H, Pelizzetti Z, et al. Processes of formation of NH4+ and NO3− ions during the photocatalyzed oxidation of N-containing compounds at the titania/water interface. Journal of Photochemistry and Photobiology A: Chemistry 1997; 102(2): 265–272. doi: https://doi.org/10.1016/S1010-6030(96)04478-4.

[57] Pignatello JJ, Oliveros E, MacKay A. Advanced oxidation processes for organic contaminant destruction based on the Fenton reaction and related chemistry. Critical Reviews in Environmental Science and Technology 2006; 36(1): 1–84. doi: 10.1080/10643380500326564.