Screening techniques as a preliminary diagnostic tool for advanced oxidative processes on a laboratory scale

Abstract

This study introduces an innovative screening approach to evaluate advanced oxidation processes (AOPs) as a preliminary diagnostic tool for degrading emerging contaminants (EC). It includes the design, prototyping, and cost-benefit analysis of circular photochemical reactors with flat and spiral internal geometries. Three-dimensional (3D) printing was used for reactor prototyping, providing flexibility and economy, and this stage was assisted by the hydrodynamic analysis of the prototypes based on residence time distribution (RTD) and macromixing models. The research evaluates the degradation of a model contaminant of emerging concern, fluoxetine (FLX) hydrochloride, using the solar/persulfate (PS) process in two water matrices (i.e., ultrapure water and sewage treatment plant effluent) to optimize reactor performance. The study also proposes primary theoretical pathways for fluoxetine degradation involving hydroxyl and sulfate radicals, as well as predicting the toxicity of the parent compound and its primary metabolites using quantitative structure-activity relationship (QSAR) models. The spiral reactor exhibits improved hydrodynamic behavior, closely resembling continuous stirred and plug flow reactors in series. Despite a slightly lower specific degradation rate in real wastewater, the solar/PS process remains effective for both matrices. By-products generated via the sulfate radical pathway are expected to be less toxic than those formed by hydroxyl radicals (HO·) attack.

Graphical abstract

Keywords

emerging contaminants / advanced oxidation process / three-dimensional printed reactor / quantum chemical calculations / toxicity

References

[1] Oppenländer T . Photochemical purification of water and air: Advanced oxidation processes (AOPs): principles, reaction mechanisms, reactor concepts. Chemistry International-Newsmagazine for IUPAC, 2003, 25(4): 31

[2] Wols B A , Harmsen D J H , Wanders-Dijk J , Beerendonk E F , Hofman-Caris C H M . Degradation of pharmaceuticals in UV (LP)/H₂O₂ reactors simulated by means of kinetic modeling and computational fluid dynamics (CFD). Water Research, 2015, 75: 11–24

[3] Psaltou S , Kaprara E , Tsaragklis A , Mitrakas M , Zouboulis A . Investigation of the removal of several micropollutants presenting different ozone reactivities from natural potable water matrix by the application of ozonation with the use of SiO₂ and Al₂O₃ as catalysts. Separations, 2022, 9(7): 173

[4] Sundar K P , Kanmani S . Progression of photocatalytic reactors and it’s comparison: a review. Chemical Engineering Research & Design, 2020, 154: 135–150

[5] Ramos B , Carneiro J G M , Nagamati L I , Teixeira A C S C . Development of intensified flat-plate packed-bed solar reactors for heterogeneous photocatalysis. Environmental Science and Pollution Research International, 2021, 28(19): 24023–24033

[6] Sharma A , Ahmad J , Flora S J S . Application of advanced oxidation processes and toxicity assessment of transformation products. Environmental Research, 2018, 167: 223–233

[7] Kowalska E , Rau S . Photoreactors for wastewater treatment: a review. Recent Patents on Engineering, 2010, 4(3): 242–266

[8] Souza L P , Sanches-Neto F O , Junior G M Y , Ramos B , Lastre-Acosta A M , Carvalho-Silva V H , Teixeira A C S C . Photochemical environmental persistence of venlafaxine in an urban water reservoir: a combined experimental and computational investigation. Process Safety and Environmental Protection, 2022, 166: 478–490

[9] Ye T , Wei Z , Spinney R , Tang C J , Luo S , Xiao R , Dionysiou D D . Chemical structure-based predictive model for the oxidation of trace organic contaminants by sulfate radical. Water Research, 2017, 116: 106–115

[10] FoglerH S. Elements of Chemical Reaction Engineering. 5th ed. New Jersey: Prentice Hall, 2016

[11] Peres J C G , Tambani P C , Teixeira A C S C , Guardani R , Vianna A S Jr . Study of an annular photoreactor with tangential inlet and outlet. II. The UV/H₂O₂ reactive flow. Chemical Engineering & Technology, 2019, 42(2): 316–326

[12] Peres J C G , de Silvio U , Teixeira A C S C , Guardani R , Vianna A S . Study of an annular photoreactor with tangential inlet and outlet: I. Fluid dynamics. Chemical Engineering & Technology, 2015, 38(2): 311–318

[13] Souza L P , Carneiro J G M , Lastre-Acosta A M , Ramos B , Teixeira A C S C . Environmental persistence of the antidepressant fluoxetine and its pharmaceutical alternative: kinetics of oxidation and mathematical simulations. Water (Basel), 2022, 14(21): 3536

[14] Singh A , Saidulu D , Gupta A K , Kubsad V . Occurrence and fate of antidepressants in the aquatic environment: insights into toxicological effects on the aquatic life, analytical methods, and removal techniques. Journal of Environmental Chemical Engineering, 2022, 10(6): 109012

[15] Lester Y , Mamane H , Zucker I , Avisar D . Treating wastewater from a pharmaceutical formulation facility by biological process and ozone. Water Research, 2013, 47(13): 4349–4356

[16] Drossou C , Petrakis Y , Tyrovola K , Xekoukoulotakis N P . Photochemical degradation of the antidepressant sertraline in aqueous solutions by UVC, UVC/H₂O₂, and UVC/S₂O₈^2–. Water Research, 2022, 217: 118442

[17] Sanches-Neto F O , Coutinho N D , Palazzetti F , Carvalho-Silva V H . Temperature dependence of rate constants for the H(D) + CH₄ reaction in gas and aqueous phase: deformed transition-state theory study including quantum tunneling and diffusion effects. Structural Chemistry, 2020, 31(2): 609–617

[18] Sanches-Neto F , Coutinho N , Aquilanti V , Silva W , Carvalho-Silva V . Mechanism and kinetics of the degradation of nitazoxanide and hydroxychloroquine drugs by hydroxyl radicals: theoretical approach to ecotoxicity. Journal of the Brazilian Chemical Society, 2023, 34(8): 1119–1129

[19] López P , Méndez F . Fukui function as a descriptor of the imidazolium protonated cation resonance hybrid structure. Organic Letters, 2004, 6(11): 1781–1783

[20] MelinJAyersP WOrtizJ V. Removing electrons can increase the electron density: a computational study of negative Fukui functions. The Journal of Physical Chemistry A, 2007, A 111: 10017–10019

[21] Lu T , Chen F . Multiwfn: a multifunctional wavefunction analyzer. Journal of Computational Chemistry, 2012, 33(5): 580–592

[22] Marenich A V , Cramer C J , Truhlar D G . Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions. Journal of Physical Chemistry B, 2009, 113(18): 6378–6396

[23] FrischM JTrucksG WSchlegelH BScuseriaG ERobbM ACheesemanJ RScalmaniGBaroneVPeterssonG ANakatsujiH, . Gaussian 16, Revision C.01. Gaussian, Inc., Wallingford CT, 2016

[24] Iuga C , Campero A , Vivier-Bunge A . Antioxidant vs prooxidant action of phenothiazine in a biological environment in the presence of hydroxyl and hydroperoxyl radicals: a quantum chemistry study. RSC Advances, 2015, 5(19): 14678–14689

[25] Zhang H , Chen L , Du P , Li F , Liu W . Unraveling different reaction characteristics of alkoxy radicals in a Co(II)-activated peracetic acid system based on dynamic analysis of electron distribution. Environmental Science & Technology, 2024, 8(7): 3506–3519

[26] Marcus R A . Electron transfer reactions in chemistry. Theory and experiment. Reviews of Modern Physics, 1993, 65(3): 599–610

[27] Reuschenbach P , Silvani M , Dammann M , Warnecke D , Knacker T . ECOSAR model performance with a large test set of industrial chemicals. Chemosphere, 2008, 71(10): 1986–1995

[28] Zhou L , Fan D , Yin W , Gu W , Wang Z , Liu J , Xu Y , Shi L , Liu M , Ji G . Comparison of seven in silico tools for evaluating of daphnia and fish acute toxicity: case study on Chinese Priority Controlled Chemicals and new chemicals. BMC Bioinformatics, 2021, 22(1): 151

[29] Leeuwen K. Technical Guidance Document on Risk Assessment, 2003

[30] Msallem B , Sharma N , Cao S , Halbeisen F S , Zeilhofer H F , Thieringer F M . Evaluation of the dimensional accuracy of 3D-printed anatomical mandibular models using FFF, SLA, SLS, MJ, and BJ printing technology. Journal of Clinical Medicine, 2020, 9(3): 817

[31] Ferro G , Polo-López M I , Martínez-Piernas A B , Fernández-Ibáñez P , Agüera A , Rizzo L . Cross-contamination of residual emerging contaminants and antibiotic resistant bacteria in lettuce crops and soil irrigated with wastewater treated by sunlight/H₂O₂. Environmental Science & Technology, 2015, 49(18): 11096–11104

[32] Sun P , Lee W N , Zhang R , Huang C H . Degradation of DEET and caffeine under UV/chlorine and simulated sunlight/chlorine conditions. Environmental Science & Technology, 2016, 50(24): 13265–13273

[33] Tan C , Jian X , Wu H , Sheng T , Sun K , Gao H . Kinetics degradation of phenacetin by solar activated persulfate system. Separation and Purification Technology, 2021, 256: 117851

[34] Cataldo F . Hydrogen peroxide photolysis with different UV light sources including a new UV-LED light source. New Frontiers in Chemistry, 2014, 23: 99–110

[35] Herrmann H . On the photolysis of simple anions and neutral molecules as sources of O^–/OH, SO_x^– and Cl in aqueous solution. Physical Chemistry Chemical Physics, 2007, 9(30): 3935–3964

[36] Wang B , Wang Y . A comprehensive review on persulfate activation treatment of wastewater. Science of the Total Environment, 2022, 831: 154906

[37] Nunes R F , Teixeira A C S C . An overview on surfactants as pollutants of concern: occurrence, impacts and persulfate-based remediation technologies. Chemosphere, 2022, 300: 134507

[38] Velo-Gala I , Pirán-Montaño J A , Rivera-Utrilla J , Sánchez-Polo M , Mota A J . Advanced oxidation processes based on the use of UVC and simulated solar radiation to remove the antibiotic tinidazole from water. Chemical Engineering Journal, 2017, 323: 605–617

[39] Yale H L . The trifluoromethyl group in medical chemistry. Journal of Medicinal and Pharmaceutical Chemistry, 1959, 1(2): 121–133

[40] Szabó L , Mile V , Kiss D J , Kovács K , Földes T , Németh T , Tóth T , Homlok R , Balogh G T , Takács E , Wojnárovits L . Applicability evaluation of advanced processes for elimination of neurophysiological activity of antidepressant fluoxetine. Chemosphere, 2018, 193: 489–497

[41] Coutinho N D , Silva V H C , de Oliveira H C B , Camargo A J , Mundim K C , Aquilanti V . Stereodynamical origin of anti-Arrhenius kinetics: negative activation energy and roaming for a four-atom reaction. Journal of Physical Chemistry Letters, 2015, 6(9): 1553–1558

[42] Coutinho N D , Sanches-Neto F O , Carvalho-Silva V H , de Oliveira H C B , Ribeiro L A , Aquilanti V . Kinetics of the OH + HCl→H₂O + Cl reaction: rate determining roles of stereodynamics and roaming and of quantum tunneling. Journal of Computational Chemistry, 2018, 39(30): 2508–2516

[43] Ramos B , Vaz W F , Diniz L F , Sanches-Neto F O , Ribeiro J C O , Carvalho-Silva V H , Teixeira A C S C , Ribeiro C , Napolitano H B , Carvalho P S Jr . Kinetics, mechanism, and tautomerism in ametryn acid hydrolysis: from molecular structure to environmental impacts. Chemosphere, 2023, 324: 138278

[44] Yang J , Lv G , Wang Z , Sun X , Gao J . Mechanisms, kinetics and eco-toxicity assessment of singlet oxygen, sulfate and hydroxyl radicals-initiated degradation of fenpiclonil in aquatic environments. Journal of Hazardous Materials, 2021, 409: 124505

[45] Amy-Sagers C , Reinhardt K , Larson D M . Ecotoxicological assessments show sucralose and fluoxetine affect the aquatic plant, Lemna minor. Aquatic Toxicology, 2017, 185: 76–85

[46] Parrott J L , Metcalfe C D . Assessing the effects of environmentally relevant concentrations of antidepressant mixtures to fathead minnows exposed over a full life cycle. Science of the Total Environment, 2019, 648: 1227–1236

[47] Pan C , Yang M , Xu H , Xu B , Jiang L , Wu M . Tissue bioconcentration and effects of fluoxetine in zebrafish (Danio rerio) and red crucian cap (Carassius auratus) after short-term and long-term exposure. Chemosphere, 2018, 205: 8–14

[48] Arnot J A , Gobas F A P C . A generic QSAR for assessing the bioaccumulation potential of organic chemicals in aquatic food webs. QSAR & Combinatorial Science, 2003, 22(3): 337–345

[49] Castillo-Zacarías C , Barocio M E , Hidalgo-Vázquez E , Sosa-Hernández J E , Parra-Arroyo L , López-Pacheco I Y , Barceló D , Iqbal H N M , Parra-Saldívar R . Antidepressant drugs as emerging contaminants: occurrence in urban and non-urban waters and analytical methods for their detection. Science of the Total Environment, 2021, 757: 143722

[50] Figuière R , Waara S , Ahrens L , Golovko O . Risk-based screening for prioritisation of organic micropollutants in Swedish freshwater. Journal of Hazardous Materials, 2022, 429: 128302

Acknowledgements

This study was financed in part by the Coordination for the Improvement of Higher Education Personnel (CAPES)—Finance Code 001. The authors thank the supports of the São Paulo Research Foundation (FAPESP) (Grant Nos. 2018/21271-6, 2019/24158-9 and 2022/13583-3), the Goiás Research Foundation (FAPEG) (Grant No. GSP2019011000037) and the National Council for Scientific and Technological Development—Brazil (CNPq) (Grant Nos. 311230/2020-2 and 309154/2023-5).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2517-y and is accessible for authorized users.

Competing interests

The authors declare that they have no competing interests.

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