Mechanistic studies of the origin of the inhibition of the photo-Fenton reaction by chloride ions

O objetivo principal deste estudo foi determinar a origem da inibição do processo foto-Fenton [Fe(II)/Fe(III), H2O2, luz UV] pelo íon cloreto. Um estudo das reações primárias da etapa fotocatalítica do processo foto-Fenton por fotólise por pulso de laser na presença de NaCl mostrou que a inibição reflete: i) fotólise competitiva dos complexos Fe(Cl)2+ e Fe(Cl)2+; ii) captura do radical hidroxila (dependente do pH) pelo íon cloreto. Esses dois processos formam o ânion radical menos reativo Cl2•- em lugar do radical HO•-, provocando uma progressiva inibição da reação de degradação com a diminuição do pH. Modelagem cinética destes resultados previa que a manutenção do pH em 3,0 durante a fotodegradação evitaria a formação do Cl2•-, o que foi confirmada através de experimentos de fotodegradação do fenol e da gasolina em meio aquoso na presença de NaCl. Por outro lado, na degradação do fenol pela reação térmica de Fenton [Fe(II)/Fe(III), H2O2], o radical hidroxila não parece ter um papel muito importante. A degradação térmica não foi inibida pela presença de íon cloreto e a cinética de mineralização do fenol pela reação térmica de Fenton é indistinguível da degradação do fenol pelo processo foto-Fenton inibido por NaCl. Isso sugere que a reação proposta por Hamilton, isto é, a redução de Fe(III) a Fe(II) por catecol (o principal intermediário inicial da oxidação do fenol) na presença de H2O2, é o mecanismo principal de catálise da reação térmica de Fenton no nosso sistema.The principal objective of the present study was to determine the origin of the inhibition of the photo-Fenton process [Fe(II)/Fe(III), H2O2, UV light] by chloride ion. A laser flash photolysis study of the primary reactions involved in the photocatalytic step of the photo-Fenton process in the presence of NaCl demonstrated that the inhibition reflects: i) competitive photolysis of the complexes Fe(Cl)2+ and Fe(Cl)2+; ii) pH-dependent sequestration of the hydroxyl radical by chloride ion. Both processes form the less reactive radical anion Cl2•- instead of HO•, resulting in a progressive inhibition of the degradation with decreasing reaction pH. Kinetic modeling of these results predicted that maintaining the pH at 3.0 throughout the reaction should prevent the formation of Cl2•-, a prediction confirmed experimentally for the photodegradation of phenol and gasoline. In contrast, in the degradation of phenol via the thermal Fenton reaction [Fe(II)/Fe(III), H2O2], the hydroxyl radical does not appear to play a very important role. Thus, the thermal degradation is not inhibited by chloride ion and the kinetics of mineralization of phenol by the thermal Fenton reaction are indistinguishable from those for degradation of phenol in the photo-Fenton reaction inhibited by NaCl. This suggests that the reaction proposed by Hamilton, i.e., reduction of Fe(III) to Fe(II) by catechol (the major initial intermediate in the oxidation of phenol) in the presence of H2O2, is the principal catalytic mechanism operative in the thermal Fenton reaction in our system

Mechanistic studies of the origin of the inhibition of the photo-Fenton reaction by chloride ions

O objetivo principal deste estudo foi determinar a origem da inibição do processo foto-Fenton [Fe(II)/Fe(III), H2O2, luz UV] pelo íon cloreto. Um estudo das reações primárias da etapa fotocatalítica do processo foto-Fenton por fotólise por pulso de laser na presença de NaCl mostrou que a inibição reflete: i) fotólise competitiva dos complexos Fe(Cl)2+ e Fe(Cl)2+; ii) captura do radical hidroxila (dependente do pH) pelo íon cloreto. Esses dois processos formam o ânion radical menos reativo Cl2•- em lugar do radical HO•-, provocando uma progressiva inibição da reação de degradação com a diminuição do pH. Modelagem cinética destes resultados previa que a manutenção do pH em 3,0 durante a fotodegradação evitaria a formação do Cl2•-, o que foi confirmada através de experimentos de fotodegradação do fenol e da gasolina em meio aquoso na presença de NaCl. Por outro lado, na degradação do fenol pela reação térmica de Fenton [Fe(II)/Fe(III), H2O2], o radical hidroxila não parece ter um papel muito importante. A degradação térmica não foi inibida pela presença de íon cloreto e a cinética de mineralização do fenol pela reação térmica de Fenton é indistinguível da degradação do fenol pelo processo foto-Fenton inibido por NaCl. Isso sugere que a reação proposta por Hamilton, isto é, a redução de Fe(III) a Fe(II) por catecol (o principal intermediário inicial da oxidação do fenol) na presença de H2O2, é o mecanismo principal de catálise da reação térmica de Fenton no nosso sistema.The principal objective of the present study was to determine the origin of the inhibition of the photo-Fenton process [Fe(II)/Fe(III), H2O2, UV light] by chloride ion. A laser flash photolysis study of the primary reactions involved in the photocatalytic step of the photo-Fenton process in the presence of NaCl demonstrated that the inhibition reflects: i) competitive photolysis of the complexes Fe(Cl)2+ and Fe(Cl)2+; ii) pH-dependent sequestration of the hydroxyl radical by chloride ion. Both processes form the less reactive radical anion Cl2•- instead of HO•, resulting in a progressive inhibition of the degradation with decreasing reaction pH. Kinetic modeling of these results predicted that maintaining the pH at 3.0 throughout the reaction should prevent the formation of Cl2•-, a prediction confirmed experimentally for the photodegradation of phenol and gasoline. In contrast, in the degradation of phenol via the thermal Fenton reaction [Fe(II)/Fe(III), H2O2], the hydroxyl radical does not appear to play a very important role. Thus, the thermal degradation is not inhibited by chloride ion and the kinetics of mineralization of phenol by the thermal Fenton reaction are indistinguishable from those for degradation of phenol in the photo-Fenton reaction inhibited by NaCl. This suggests that the reaction proposed by Hamilton, i.e., reduction of Fe(III) to Fe(II) by catechol (the major initial intermediate in the oxidation of phenol) in the presence of H2O2, is the principal catalytic mechanism operative in the thermal Fenton reaction in our system

Transferência de energia entre corantes catiônicos em sistemas homogêneos

In this work, the energy transfer by dipole-dipole interaction between cationic dyes in n-alcohols (methanol, ethanol, 1-propanol and 1-butanol) is studied by time resolved and steady state fluorescence measurements. The critical radii of energy transfer were determined by three independent methods; the spectral overlap, fluorescence decay profiles, and relative intensity measurements. In all solvents, R0 values of the dye pairs obtained from spectral overlap were between 40 to 90 Å. Steady state and time resolved fluorescence measurements resulted in values of R0 in the range of 50 - 80 Å, with good correlation of values

Can activated sludge treatments and advanced oxidation processes remove organophosphorus flame retardants?

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)This study aims to determine the occurrence of 10 OPFRs (including chlorinated, nonchlorinated alkyl and aryl compounds) in influent, effluent wastewaters and partitioning into sludge of 5 wastewater treatment plants (WWTP) in Catalonia (Spain). All target OPFRs were detected in the WWTPs influents, and the total concentration ranged from 3.67 mu g L-1 to 150 mu g L-1. During activated sludge treatment, most OPFRs were accumulated in the sludge at concentrations from 35.3 to 9980 ng g(-1) dw. Chlorinated compounds tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP) and tris(2,3-dichloropropyl) phosphate (TDCPP) were not removed by the conventional activated sludge treatment and they were released by the effluents at approximately the same inlet concentration. On the contrary, aryl compounds tris(methylphenyl) phosphate (TMPP) and 2-ethylhexyl diphenyl phosphate (EHDP) together with alkyl tris(2-ethylhexyl) phosphate (TEHP) were not detected in any of the effluents. Advanced oxidation processes (UV/H2O2 and O-3) were applied to investigate the degradability of recalcitrant OPFRs in WWTP effluents. Those detected in the effluent sample (TCEP, TCIPP, TDCPP, tributyl phosphate (TNBP), tri-iso-butyl phosphate (TIBP) and tris(2-butoxyethyl) phosphate (TBOEP)) had very low direct UV-C photolysis rates. TBOEP, TNBP and TIBP were degraded by UV/H2O2 and O-3. Chlorinated compounds TCEP, TDCPP and TCIPP were the most recalcitrant OPFR to the advanced oxidation processes applied. The study provides information on the partitioning and degradability pathways of OPFR within conventional activated sludge WWTPs. (C) 2015 Elsevier Inc. All rights reserved.This study aims to determine the occurrence of 10 OPFRs (including chlorinated, nonchlorinated alkyl and aryl compounds) in influent, effluent wastewaters and partitioning into sludge of 5 wastewater treatment plants (WWTP) in Catalonia (Spain). All targe144A1118CNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORFUNDECT - FUNDAÇÃO DE APOIO AO DESENVOLVIMENTO DO ENSINO, CIÊNCIA E TECNOLOGIA DO ESTADO DE MATO GROSSO DO SULConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)sem informaçãosem informaçãosem informaçãoThe authors wish to thank the Brazilian funding agencies CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico), CAPES (Coordenação de Aperfeiçoamento de Pessoal de Nível Superior), FUNDECT (Fundação de Apoio ao Desenvolvimento do Ensino, C

Photocatalytic mechanism of metoprolol oxidation by photocatalysts TiO2 and TiO2 doped with 5% B: primary active species and intermediates

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)In photocatalysis, controversy still exists over as whether oxidation proceeds via primary oxidants, such as HO center dot radicals, positive holes, electrons, O-2(center dot)-radicals in the photodegradation process. The contribution of the main active species to the photocatalytic degradation of metoprolol (MET) using a solar simulator with Xenon lamp as irradiation source was examined by using different specific scavengers (formic acid, tert-butyl alcohol, rho-benzoquinone and oxygen). According to this, we also compared the effect on the generation of active species, in the MET degradation, of two types of TiO2 catalyst having different physical and chemical properties: pure TiO2 and TiO2 doped with 5% B (w/w), both synthesized by sol-gel method. The scavenger study indicates that HO center dot radicals are the dominant reactive species, contributing around 80% and to a lesser extent by the contribution of O-2(center dot)- radicals and holes in systems using TiO2 doped with 5% B (w/w). However, when pure TiO2 was used as catalyst, experiments carried out in rho-benzoquinone demonstrate that O-2(center dot)-radicals did not participate in the degradation mechanism of MET. Oxygen seems to play an important role during the observed degradation of MET. Additionally, the relation between the intermediates formed during the photocatalytic degradation with TiO2 doped 5% B (w/w) as catalyst, with addition of specific scavengers, was investigated and distinct degradation pathways have been proposed for each active species involved. By-products studies in the presence of scavengers were used as a diagnostic tool for the analysis of the photocatalytic mechanism and it was possible to prove that there is change in the reactions of the degradation process of MET when change the role of any active species generated on the surface of the catalyst. (C) 2016 Elsevier B.V. All rights reserved.In photocatalysis, controversy still exists over as whether oxidation proceeds via primary oxidants, such as HO radicals, positive holes, electrons, O2− radicals in the photodegradation process. The contribution of the main active species to the photocata194111122CNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORFUNDECT - FUNDAÇÃO DE APOIO AO DESENVOLVIMENTO DO ENSINO, CIÊNCIA E TECNOLOGIA DO ESTADO DE MATO GROSSO DO SULConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)sem informaçãosem informaçãosem informaçãoThe authors wish to thank the Brazilian funding agencies CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico), CAPES (Coordenação de Aperfeiçoamento de Pessoal de Nível Superior), FUNDECT (Fundação de Apoio ao Desenvolvimento do Ensino, C

Tolfenamic acid degradation by direct photolysis and the UV-ABC/H2O2 process: factorial design, kinetics, identification of intermediates, and toxicity evaluation

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)This study employed direct UV-ABC photolysis and the UV-ABC/H2O2 process to investigate the degradation of tolfenamic add (TA), a common anti-inflammatory drug used in both human and veterinary medicine. A 23 factorial design with added center point was used to evaluate the effect of three independent variables namely, H2O2 concentration ([H2O2]), TA concentration ([TA]), and experiment time (time) on TA degradation and H2O2 photolysis during UV-ABC/H2O2 treatment using a high-pressure mercury vapor lamp (photon flux of 2.6307 x 10(4) J s(-1)) as the UV irradiation source. The responses yielded similar values, revealing a linear behavior, with correlation coefficients R = 0.9968 and R-adj = 0.9921 for TA degradation and R = 0.9828 and Radj = 0.9570 for H2O2 photolysis. The most efficient combination of variables was [H2O2] = 255 mg L-1 and [TA] = 25 mg L-1, resulting in 100% TA degradation and 98.87%H2O2 photolysis by 90 min of treatment. Additionally, the second order kinetic constant of the reaction between TA and HO center dot was determined using a competitive kinetic model, employing 2,4-dichlorophenoxyacetic acid (2,4D) as the reference compound. The kinetic constant was 1.9 x 1010 1 s-1 in alkaline medium. TA degradation by direct photolysis generated quinone imines as by products, responsible for the formation of a dark red "internal filter" that increased the value of acute toxicity to Artemia saline. The UV-ABC/H2O2 process did not promote formation of quinone imines by 90 min of treatment and therefore did not increase acute toxicity values. Several by-products generated during TA degradation were identified and possible degradation pathways for the UV-ABC and UV-ABC/H2O2 processes were proposed. (C) 2016 Elsevier B.V. All rights reserved.This study employed direct UV-ABC photolysis and the UV-ABC/H2O2 process to investigate the degradation of tolfenamic add (TA), a common anti-inflammatory drug used in both human and veterinary medicine. A 23 factorial design with added center point was u573518531CNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORFUNDECT - FUNDAÇÃO DE APOIO AO DESENVOLVIMENTO DO ENSINO, CIÊNCIA E TECNOLOGIA DO ESTADO DE MATO GROSSO DO SULConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)sem informaçãosem informaçãosem informaçãoThe authors wish to thank the Brazilian funding agencies Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq), Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (Capes), and Fundação de Apoio ao Desenvolvimento do Ensino, Ciênci