title: Photolysis of model emerging contaminants in ultra-pure water: kinetics, by-products formation and degradation pathways.
abstract: The photolysis of five frequent emerging contaminants (Benzotriazole, Chlorophene, N,N-diethyl-m-toluamide or DEET, Methylindole, and Nortriptyline HCl) was investigated in ultrapure water under monochromatic ultraviolet radiation at 254 nm and by a combination of UV and hydrogen peroxide. The results revealed that the photolysis rates followed first-order kinetics, with rate constant values depending on the nature of the specific compound, the pH, and the presence or absence of the scavenger tert-butanol. Quantum yields were also determined and values in the range of 53.8 × 10⁻³ - 9.4 × 10⁻³ mol E⁻¹ for Benzotriazole, 525 × 10⁻³ - 469 × 10⁻³ mol E⁻¹ for Chlorophene, 2.8 × 10⁻³ - 0.9 × 10⁻³ mol E⁻¹ for DEET, 108 × 10⁻³ - 165 × 10⁻³ mol E⁻¹ for Methylindole, and 13.8 × 10⁻³ - 15.0 × 10⁻³ mol E⁻¹ for Nortriptyline were obtained. The study also found that the UV/H₂O₂ process enhanced the oxidation rate in comparison to direct photolysis. High-performance liquid chromatography coupled to electrospray ionization quadrupole time-of-flight mass spectrometry (HPLC-ESI-QTOF-MS) technique was applied to the concentrations evaluation and further identification of the parent compounds and their by-products, which allowed the proposal of the degradation pathways for each compound. Finally, in order to assess the aquatic toxicity in the photodegradation of these compounds, the Vibrio fischeri acute toxicity test was used, and the results indicated an initial increase of this parameter in all cases, followed by a decrease in the specific case of Benzotriazole, DEET, Methylindole, and Chlorophene.
authors.affiliation: Departamento de Ingeniería Química, Universidad de Extremadura, Facultad de Ciencias, 06071 Badajoz, Spain. javben@unex.es
authors.forename: F Javier
authors.initials: FJ
authors.lastname: Benitez
authors.forename: Juan L
authors.initials: JL
authors.lastname: Acero
authors.forename: Francisco J
authors.initials: FJ
authors.lastname: Real
authors.forename: Gloria
authors.initials: G
authors.lastname: Roldan
authors.forename: Elena
authors.initials: E
authors.lastname: Rodriguez
mesh_terms: D048908:Aliivibrio fischeri / Q000187:drug effects / Q000254:growth & development; D000891:Anti-Infective Agents, Local / Q000032:analysis / Q000737:chemistry / Q000633:toxicity; D000929:Antidepressive Agents, Tricyclic / Q000032:analysis / Q000737:chemistry / Q000633:toxicity; D003671:DEET / Q000032:analysis / Q000737:chemistry; D004003:Dichlorophen / Q000031:analogs & derivatives / Q000032:analysis; D016166:Free Radical Scavengers / Q000737:chemistry; D006861:Hydrogen Peroxide / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D007302:Insect Repellents / Q000032:analysis / Q000737:chemistry / Q000633:toxicity; D007700:Kinetics; D008956:Models, Chemical; D009661:Nortriptyline / Q000032:analysis / Q000737:chemistry / Q000633:toxicity; D016877:Oxidants / Q000737:chemistry; D010084:Oxidation-Reduction; D010782:Photolysis; D012862:Skatole / Q000633:toxicity; D014230:Triazoles / Q000032:analysis / Q000633:toxicity; D014466:Ultraviolet Rays; D014867:Water / Q000737:chemistry*; D014874:Water Pollutants, Chemical / Q000032:analysis* / Q000737:chemistry / Q000633:toxicity; D018508:Water Purification / Q000379:methods*; D020002:tert-Butyl Alcohol / Q000737:chemistry
chemical_list: D000891:Anti-Infective Agents, Local; D000929:Antidepressive Agents, Tricyclic; D016166:Free Radical Scavengers; D007302:Insect Repellents; D016877:Oxidants; D014230:Triazoles; D014874:Water Pollutants, Chemical; D014867:Water; D003671:DEET; C004660:clorophene; C012771:benzotriazole; D012862:Skatole; D006861:Hydrogen Peroxide; D009661:Nortriptyline; D020002:tert-Butyl Alcohol; D004003:Dichlorophen