Agrochemicals such as the insecticide Fipronil that bear fluoro groups are generally fat-soluble and nearly insoluble in water, so that their photodegradation in a heterogeneous aqueous gallium oxide dispersion presents some challenges. This article examined the photodegradation of this insecticide by solubilizing it through the addition of organic solvents (EtOH, MeOH, THF, 1,4-dioxane and ethylene glycol) to an aqueous medium and then subjecting the insecticide to 254 nm UVC radiation under photocatalytically inert (Ga2O3/N2) and air-equilibrated (Ga2O3/O2) conditions, as well as photochemically in the absence of Ga2O3 but also under inert and air-equilibrated conditions. Defluorination, dechlorination, desulfonation and denitridation of Fipronil were examined in mixed aqueous/organic media (10, 25 and 50 vol% in organic solvent).
View Article and Find Full Text PDFPersistent fluorinated substances, such as the fluorine-bearing pharmaceutical drugs Fluoxetine (FLX; Prozac) and Fluvoxamine maleate (FOM) together with several other substrates (fluorobenzoic acid and fluoroaliphatic model compounds), were photochemically defluorinated and degraded under UVC illumination in relatively good yields in the presence of a wide band gap metal oxide (β-Ga2O3) in heterogeneous aqueous media. The formation of fluoride ions increased with increasing illumination time under an inert nitrogen atmosphere, the transformation of the aromatic moiety was slower under these conditions, but nonetheless it did occur. The optimal amount of β-Ga2O3 loading for defluorination was 50 mg in aqueous media (0.
View Article and Find Full Text PDFThis article examines the oxidative disposal of Prozac(®) (also known as Fluoxetine, FXT) through several oxidative processes with and without UV irradiation: for example, TiO(2) alone, O(3) alone, and the hybrid methods comprised of O(3) + H(2)O(2) (PEROXONE process), TiO(2) + O(3) and TiO(2) + O(3) + H(2)O(2) at the laboratory scale. Results show a strong pH dependence of the adsorption of FXT on TiO(2) and the crucial role of adsorption in the whole degradation process. Photolysis of FXT is remarkable only under alkaline pH.
View Article and Find Full Text PDFA tubular-type solar photoreactor system powered by commercial solar panels and consisting of six 20-tube modules (Pyrex glass) to mimic a pilot plant scale configuration was designed and constructed to examine the remediation of simulated wastewaters contaminated with various classes of organic pollutants such as endocrine disruptors (e.g. bisphenol A), anionic surfactants (sodium butylnaphthalenesulfonate and sodium dodecyl- benzenesulfonate), herbicides (e.
View Article and Find Full Text PDFWe have studied the photocatalytic transformation of atenolol, 4-[2-hydroxy-3-[(1-methyl)amino]propoxyl]benzeneacetamide, a cardioselective beta-blocking agent used to treat cardiac arrhythmias and hypertension, under simulated solar irradiation using titanium dioxide as photocatalyst. The investigation involved monitoring drug decomposition, identifying intermediate compounds, assessing mineralization, and evaluating toxicity. High-performance liquid chromatography (HPLC) coupled to high-resolution mass spectrometry (HRMS) via an electrospray ionization (ESI) interface was a powerful tool for the identification and measurement of the degradation products; 23 main species were identified.
View Article and Find Full Text PDFThe DNA damage caused by TiO2 under in vitro conditions by UV-A exposure in the presence of anionic vesicles of Aerosol OT (AOT) was investigated. The supercoiled form (S) in DNA plasmids was converted to the linear form (L) via the relaxed form (R). The DNA damage was slower in the presence of AOT vesicles prepared in aqueous NaCl solution.
View Article and Find Full Text PDFMicrowave-assisted dechlorination of chlorobenzene and the three dichlorobenzenes takes place in the presence of the hypophosphite (NaH(2)PO(2)) reductant and Pd-loaded activated carbon (Pd/C) in alkaline media at relatively low temperatures. The extent of loss/dechlorination at 90 degrees C followed the order: o-DCB approximately m-DCB>CB>p-DCB. Detected final products were mostly benzene and phenol.
View Article and Find Full Text PDFThe UV-photon-induced degradation of heptafluorobutanoic acid was investigated in acidic aqueous solutions in the presence of titanium dioxide. Heptafluorobutanoic acid could be degraded with this photocatalyst in a light-induced reaction generating carbon dioxide and fluoride anions. Carbon dioxide evolution in a significant amount occurred only in the presence of molecular oxygen and the photocatalyst.
View Article and Find Full Text PDFThe light-induced degradation of alkylurea derivatives under simulated solar irradiation has been investigated in aqueous solutions containing TiO(2) as a photocatalyst. Herein, we will focus on how the presence of one or more methyl (or ethyl) groups on urea modifies the kinetics of disappearance and influences both the ratio and the extent of the inorganic nitrogen formation caused by different degradation pathways. In the present work, we have elucidated a mechanism for the formation of transformation products of the alkyl derivatives by combining several analytical and spectroscopic procedures and the theoretical simulation of ab initio calculations.
View Article and Find Full Text PDFAmitrole (ATz, 3-amino-1H-1,2,4-triazole) is a widely employed herbicide with strong estrogenic activity that can lead to abnormalities of the thyroid gland and can cause mutations. The photocatalytic transformation of ATz was carried out at the UV-irradiated TiO2/H2O interface, along with the triazole derivatives Tz (1H-1,2,4-triazole) and DaTz (3,5-diamino-1H-1,2,4-triazole) to assess the decomposition of these herbicides, to identify intermediates, and to elucidate some mechanistic details of the ATz degradation. Conversion of the nitrogens of these triazoles to NH4+ and/ or NO3- ions occurs competitively and depends on the number of amine functions on the five-membered triazole rings.
View Article and Find Full Text PDFThermal and nonthermal effects originating when a system is subjected to a microwave radiation field in the TiO2-photocatalyzed transformation of model substances containing various functional groups (e.g., benzoic acid, phthalic acid, o-formylbenzoic acid, phthalaldehyde, succinic acid, dimethyl phthalate, diethyl phthalate, and phenol) have been examined under simultaneous irradiation by ultraviolet (UV) and microwave (MW) radiations.
View Article and Find Full Text PDFA representative polyoxometalate, alpha-12-tungstophosphatic acid (PW12(3-), POM), is loaded on the surface of TiO2 particles used as a cocatalyst to gain further insights into the underlying reaction mechanism and to estimate the feasibility of using the new POM/TiO2 cocatalyst in the photocatalytic degradation of 2,4-dichlorophenol (DCP) in aqueous media. Loading the PW12(3-) species on the surface of TiO2 enhances charge separation in the UV-illuminated TiO2, thereby accelerating the hydroxylation of the initial DCP substrate but not the mineralization of DCP, which is somewhat suppressed in the presence of the polyoxometalate. An increase in the load of POM increases the concentration of aromatic intermediates, and more toxic intermediates, such as 2,6-dichlorodibenzo-p-dioxin, 2,4,6-trichlorophenol, are detected in the PW12(3-)/TiO2 system.
View Article and Find Full Text PDFThe photocatalyzed degradation (PD) of the cationic rhodamine-B (RhB) dye was examined in aqueous TiO2 dispersions using UV/Vis illumination assisted by microwave radiation (PD/MW). The initial degradation by the PD/MW method is compared to the PD method and to the thermally assisted PD method using conventional heating (PD/TH). Total organic carbon (TOC) assays show that the efficiency of complete mineralization of the dye follows PD/MW > PD/TH > PD > MW.
View Article and Find Full Text PDFThe titanium dioxide photocatalyst is employed to examine the influence of chemisorbed hexachloroplatinate(IV) anions (PtCl(6) (2-)) on the surface of P-25 TiO(2) particles on the photoinduced conversion of the azo dye Ethyl Orange (EO) in visible light-illuminated Pt(IV)/TiO(2) dispersions. Spin-trap electron spin resonance (ESR) spectral results, measurement of quantities of organoperoxides formed, total organic carbon (TOC) and chemical oxygen demand (COD(Cr)) assays, together with XPS evidence show that the self-sensitized transformation dynamics of the EO dye mediated by Pt(IV)/TiO(2) are much faster than those occurring on naked TiO(2) under otherwise identical conditions of visible light irradiation. X-ray photoelectron spectral data also show that under the experimental conditions used, no Pt(0) formed on the titania particles during visible light irradiation.
View Article and Find Full Text PDFBisphenol A (BPA) can be decomposed photocatalytically under UV-illumination in aqueous TiO2 dispersion. The two methyl groups in BPA were initially attacked with .OH and/or .
View Article and Find Full Text PDFThe photostabilities of a random set of commercially available sunscreen lotions and their active ingredients are examined spectroscopically subsequent to simulated sunlight UV exposure. Loss of filtering efficacy can occur because of possible photochemical modifications of the sunscreen active agents. Changes in absorption of UVA/ UVB sunlight by agents in sunscreen lotions also leads to a reduction of the expected photoprotection of human skin and DNA against the harmful UV radiation.
View Article and Find Full Text PDFStrong oxidation by titanium dioxide photocatalysis can occur by photodegradation of organic contaminants in air and water. Some endocrine disruptors such as 2,4-dichlorophenoxy acetic acid (;;; ), 2,4-dichlorophenol (;;; ), nonylphenol (; ), bisphenol A (), diethyl phthalate (; ), etc. which can be neither biodegraded by bacteria nor degraded thermally can be degraded by TiO(2) photocatalytic treatment.
View Article and Find Full Text PDFThe characteristic features of a novel double-quartz cylindrical plasma photoreactor (DQCPP) were assessed by examining the photodegradation of rhodamine-B dye (RhB+) in aqueous TiO2 dispersions irradiated simultaneously by both microwave radiation and UV/visible radiation emitted from a microwave-powered (MW, 2.45 GHz) electrodeless mercury lamp. The features of the DQCPP lamp are given and discussed in terms of the experimental output UV energy in the wavelength ranges 210-300 and 310-400 nm for applied MW powers from 74 to 621 W.
View Article and Find Full Text PDFThe photodegradation of dye pollutants under visible light irradiation in TiO2 dispersions continues to draw considerable attention because of the greater effective utilization of solar energy and its potential application in treating wastewaters from textile and photographic industries. To get a better handle on the mechanistics details of this TiO2-assisted photodegradation of dyes with visible radiation, the process was examined by UV-visible spectroscopy, high-performance liquid chromatography, silica gel thin-layer chromatography, and matrix-assisted laser desorption ionization time-of-flight mass spectrometric techniques to separate and identify the N-de-ethylated intermediate products during the photodegradation of N,N,N,N-tetraethylsulforhodamine-B (SRB) in the absence and presence of iodide ions. Five intermediates, namely, N,N-diethyl-N'-ethyl-sulforhodamine, N,N-diethylsulforhodamine, N-ethyl-N'-ethylsulforhodamine, N-ethylsulforhodamine, and sulforhodamine were thus identified.
View Article and Find Full Text PDFThe photocatalytic decomposition of the cationic rhodamine-B (RhB) dye was examined in aqueous TiO2 dispersions using an integrated microwave/UV-illumination (PD/MW) method. This procedure proved to be superior in the degradation of the dye than the TiO2 photocatalytic degradative method alone. With few exceptions, the integrated PD/MW method also proved superior for other chemical systems.
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