Comparisons of polychromatic and monochromatic UV-based treatments of bisphenol-A in water via toxicity assessments

Polychromatic ultraviolet irradiation, such as from medium pressure (MP) Hg lamps may enhance the UV degradation of environmental pollutants as compared to low pressure (LP) Hg UV sources emitting monochromatic irradiation. Typically, studies involving destruction of environmental pollutants such as endocrine disrupting compounds (EDCs) are based on measurement of the parent compound decay using analytical chemistry, but such information is insufficient to determine an effective treatment endpoint because the identity and biological activity of many transformation products remain unknown. Bioanalytical methods to assess residual biological activity of a treated water offers one means to compare removal efficiency of EDC activity between MP- and LP-UV lamps under photolysis and UV/H2O2 oxidation. In this study, changes in estrogenic activity of bisphenol-A (BPA) as a function of UV treatment were evaluated using both an in vitro yeast estrogen screen and in vivo vitellogenin assay with Japanese medaka (Oryzias latipes) fish. Decay of BPA parent compound and formation of degradation products were followed using HPLC analysis. Results demonstrated that MP-UV direct photolysis more effectively removed BPA and associated estrogenic activity compared to LP-UV lamps. UV in combination with H2O2 significantly removed estrogenic activity in vitro and in vivo compared to direct photolysis; however, no significant difference in removal rates was found between the two lamps under UV/H2O2 oxidation. Furthermore, the UV/H2O2 process was effective for reducing embryo toxicity of BPA, but resulted in the production of acidic intermediates, causing acute toxicity and delayed hatching in some medaka embryos.     

Biological assessment of bisphenol A degradation in water following direct photolysis and UV advanced oxidation

Endocrine disrupting compounds (EDCs) are exogenous environmental chemicals that can interfere with normal hormone function and present a potential threat to both environmental and human health. The fate, distribution and degradation of EDCs is a subject of considerable investigation. To date, several studies have demonstrated that conventional water treatment processes are ineffective for removal of most EDCs and in some instances produce multiple unknown transformation products. In this study we have investigated the use of direct photolysis with low-pressure (LP) Hg UV lamps and UV+hydrogen peroxide (H(2)O(2)) advanced oxidation process (AOP) for the degradation of a prototypic endocrine disrupter, bisphenol A (BPA), in laboratory water. Removal rates of BPA and formation of degradation products were determined by high performance liquid chromatography (HPLC) analysis. Changes in estrogenic activity were evaluated using both in vitro yeast estrogen screen (YES) and in vivo vitellogenin (VTG) assays with Japanese medaka fish (Oryzias latipes). Our results demonstrate that UV alone did not effectively degrade BPA. However, UV in combination with H(2)O(2) significantly removed BPA parent compound and aqueous estrogenic activity in vitro and in vivo. Removal rates of in vivo estrogenic activity were significantly lower than those observed in vitro, demonstrating differential sensitivities of these bioassays and that certain UV/AOP metabolites may retain estrogenic activity. Furthermore, the UV/H(2)O(2) AOP was effective for reducing larval lethality in treated BPA solutions, suggesting BPA degradation occurred and that the degradation process did not result in the production of acutely toxic intermediates.     

Photooxidation of naphthalenesulfonic acids: comparison between processes based on O(3), O(3)/activated carbon and UV/H(2)O(2)

The aim of the present study was to analyze and compare the efficacy of UV photodegradation with that of different advanced oxidation processes (O(3), UV/H(2)O(2), O(3)/activated carbon) in the degradation of naphthalenesulfonic acids from aqueous solution and to investigate the kinetics and the mechanism involved in these processes. Results obtained showed that photodegradation with UV radiation (254 nm) of 1-naphthalenesulfonic, 1,5-naphthalendisulfonic and 1,3,6-naphthalentrisulfonic acids is not effective. Presence of duroquinone and 4-carboxybenzophenone during UV irradiation (308-410 nm) of the naphthalenesulfonic acids increased the photodegradation rate. Addition of H(2)O(2) during irradiation of naphthalenesulfonic acids accelerated their elimination, due to the generation of ()OH radicals in the medium. Comparison between UV photodegradation 254 m and the advanced oxidation processes (O(3), O(3)/activated carbon and UV/H(2)O(2)) showed the low-efficacy of the former in the degradation of these compounds from aqueous medium. Thus, among the systems studied, those based on the use of UV/H(2)O(2) and O(3)/activated carbon were the most effective in the oxidation of these contaminants from the medium. This is because of the high-reactivity of naphthalenesulfonic acids with the *OH radicals generated by these two systems. This was confirmed by the values of the reaction rate constant of *OH radicals with these compounds k(OH), obtained by competitive kinetics (5.7 x 10(9) M(-1) s(-1), 5.2 x 10(9) M(-1) s(-1) and 3.7 x 10(9) M(-1) s(-1) for NS, NDS and NTS, respectively).     

光催化降解水体异味物质2-MIB的机理

以水体异味物质2-甲基异莰醇(2-methylisoborneol,2-MIB)为研究对象,在紫外光(λ<380 nm)照射下,探讨TiO2(P25)对2-MIB的光催化降解特性及光化学作用机理。结果表明,UV/TiO2光催化体系可以有效去除水体异味物质2-MIB,紫外光照射60 min,对2-MIB的降解率达95%。同时研究了光催化降解体系介质pH,共存腐殖酸(HA)和过硫酸钾(K2S2O8)对UV/TiO2光催化体系降解2-MIB的影响,发现低浓度HA([HA]≤0.5 mg/L)可以提高2-MIB降解速率,当HA浓度高于0.5 mg/L,2-MIB降解反应受到抑制;同时当加入电子受体K2S2O8后,降解体系中活性物种羟基自由基(.OH)明显增加,提高了TiO2对2-MIB的降解能力。利用苯甲酸荧光光度法和POD-DPD显色法跟踪测定降解过程中羟基自由基(·OH)和过氧化氢(H2O2)的变化,表明光催化反应涉及·OH机理。     

Contribution of free radicals to chlorophenols decomposition by several advanced oxidation processes

The chemical decomposition of aqueous solutions of various chlorophenols (4-chlorophenol (4-CP), 2,4-dichlorophenol (2-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP)), which are environmental priority pollutants, is studied by means of single oxidants (hydrogen peroxide, UV radiation, Fenton's reagent and ozone at pH 2 and 9), and by the Advanced Oxidation Processes (AOPs) constituted by combinations of these oxidants (UV/H2O2 UV/Fenton's reagent and O3/UV). For all these reactions the degradation rates are evaluated by determining their first-order rate constants and the half-life times. Ozone is more reactive with higher substituted CPs while OH* radicals react faster with those chlorophenols having lower number of chlorine atoms. The improvement in the decomposition levels reached by the combined processes, due to the generation of the very reactive hydroxyl radicals. in relation to the single oxidants is clearly demonstrated and evaluated by kinetic modeling.     

Oxidative degradation of dimethylsulfoxide by locally concentrated hydroxyl radicals in streamer corona discharge process

This study systematically investigates the characteristic degradation behaviors of dimethylsulfoxide (DMSO) by the streamer corona discharge process (SCDP) in water. The analysis of the oxidized intermediates of DMSO shows that hydroxyl radical (*OH) is the main oxidant responsible for the degradation of DMSO in the SCDP. The various experiments on the degradation and mineralization of DMSO, and the effect of the *OH scavenger suggest that the SCDP produces locally concentrated *OHs in and around the plasma channel. This explanation was also supported by the formation of H(2)O(2) and the effect of the *OH scavenger on the H(2)O(2) production rate in the SCDP. Based on the kinetic data for the degradation of DMSO and the production of H(2)O(2) in the SCDP, the volume of the active region in which the *OHs are concentrated, and the effective concentration of *OH in that region were estimated to be 0.21 microl and 5.0 x 10(-3)M, respectively. This level of *OH concentration in the SCDP is approximately 10(7)-10(9) times higher than that generated in ordinary advanced oxidation processes using *OH. The ramifications of the results obtained in this study on successful water treatment using the SCDP are also discussed.     

Hydroxyl radical concentration profile in photo-Fenton oxidation process: generation and consumption of hydroxyl radicals during the discoloration of azo-dye Orange II

Dynamic behaviors of hydroxyl (OH) radical generation and consumption in photo-Fenton oxidation process were investigated by measuring OH radical concentration during the discoloration of azo-dye Orange II. The effects of operating parameters for photo-Fenton discoloration, i.e. dosages of H₂O₂ and Fe, initial dye concentration, solution pH and UV irradiation, on the generation and consumption of OH radicals playing the main role in advanced oxidation processes were extensively studied. The scavenger probe or trapping technique in which coumarin is scavenger of OH radical was applied to estimate OH radical concentration in the photoreactor during the photo-Fenton discoloration process. The OH radical generation was enhanced with increasing the dosages of Fenton regents, H₂O₂ and Fe. At the initial stage of photo-Fenton discoloration of Orange II, the OH radical concentration rapidly increased (Phase-I) and the OH radical concentration decreased after reaching of OH radical concentration at maximum value (Phase-II). The decrease in OH radical concentration started when the complete discoloration of Orange II was nearly achieved and the H₂O₂ concentration became rather low. The dynamic behavior of OH radical concentration during the discoloration of Orange II was found to be strongly linked with the change in H₂O₂ concentration. The generation of OH radical was maximum at solution pH of 3.0 and decreased with an increase of solution pH. The OH radical generation rate in the Fenton Process was rather slower than that in the photo-Fenton process.     

Synergy of ozonation and photocatalysis to mineralize low concentration 2,4-dichlorophenoxyacetic acid in aqueous solution

Concentration of 2,4-dichlorophenoxyacetic acid (2,4-D) may affect its degradation kinetics in advanced oxidation systems, and combinations of two or more systems can be more effective for its mineralization at low concentration levels. Degradations and mineralizations of 0.045mM 2,4-D using O(3), O(3)/UV, UV/TiO(2) and O(3)/UV/TiO(2) systems were compared, and influence of reaction temperature on the mineralization in O(3)/UV/TiO(2) system was investigated. 2,4-D degradations by O(3), O(3)/UV and UV/TiO(2) systems were similar to the results of earlier investigations with higher 2,4-D concentrations. The degradations and total organic carbon (TOC) removals in the four systems were well described by the first-order reaction kinetics. The degradation and removal were greatly enhanced in O(3)/UV/TiO(2) system, and further enhancements were observed with larger O(3) supplies. The enhancements were attributed to hydroxyl radical (()OH) generation from more than one reaction pathway. The degradation and removal in O(3)/UV/TiO(2) system were very efficient with reaction temperature fixed at 20 degrees C. It was suspected that reaction temperature might have influenced ()OH generation in the system, which needs further attention.     

Homogeneous degradation of 1,2,9,10-tetrachlorodecane in aqueous solutions using hydrogen peroxide, iron and UV light

The homogeneous degradation of the polychlorinated n-alkane, 1,2,9,10-tetrachlorodecane (T4C10), was studied in aqueous solutions of hydrogen peroxide, including Fenton and photo-Fenton reaction conditions. All solutions were adjusted to a pH of 2.8 and an ionic strength of 0.1 M NaClO4 prior to photolysis. T4C10 (2 x 10(-6) M) was substantially degraded by the H2O2/UV system (1.0 x 10(-2) M H2O2), with 60% disappearance in 20 min of irradiation in a photoreactor equipped with 300 nm lamps of light intensity 3.6 x 10(-5) Ein L(-1) min(-1) (established by ferrioxalate actinometry). The reaction produced stoichiometric amounts of chloride ion indicating complete dechlorination of the chlorinated n-alkane. T4C10 degraded very slowly under Fenton (Fe2+/H2O2/dark) and Fenton-like (Fe3+/H2O2/dark) conditions. However, when the same solutions were irradiated, T4C10 degraded more rapidly than in the H2O2/UV system, with 61% disappearance in 10 min of exposure. The rapid degradation is related to the enhanced degradation of hydrogen peroxide to oxidizing *OH radicals under photo-Fenton conditions. Degradation was inhibited in both the H2O2/UV and photo-Fenton systems by the addition of KI and tert-butyl alcohol due to *OH scavenging.     

Quantitation of Hydroxyl Radicals from Photolysis of Fe(III)-Citrate Complexes in Aerobic Water (5 pp)

Background For their high photoreactivity, Fe(III)-carboxylate complexes are important sources of H2O2 for some atmospheric and surface waters. Citrate is one kind of carboxylate, which can form complexes with Fe(III). In our previous study, we have applied Fe(III)-citrate complexes to degrade and decolorize dyes in aqueous solutions both under UV light and sunlight. Results have shown that carboxylic acids can promote the photodegradation efficiency. It is indicated that the photolysis of Fe(III)-citrate complexes may cause the formation of some reactive species (e. g. H2O2 and ·OH). This work is attempted to quantify hydroxyl radicals generated in the aqueous solution containing Fe(III)-citrate complexes and to interpret the photoreactivity of Fe(III)-citrate complexes for degrading organic compounds. Methods By using benzene as the scavenger to produce phenol, the photogeneration of ·OH in the aqueous solution containing Fe (III)-citrate complexes was determined by HPLC. Results and Discussion In the aqueous solution containing 60.0/30.0 mM Fe(III)/citrate and 7.0 mM benzene at pH 3.0, 96.66 mM ·OH was produced after irradiation by a 250W metal halide light (l ≥ 313 nm) for 160 minutes. Effects of initial pH value and concentrations of Fe(III) and citrate on ·OH radical generation were all examined. The results show that the greatest photoproduction of ·OH in the aqueous solution (pH ranged from 3.0 to 7.0) was at pH 3.0. The photoproduction of ·OH increased with increasing Fe(III) or citrate concentrations. Conclusion In the aqueous solutions containing Fe(III)-citrate complexes, ·OH radicals were produced after irradiation by a 250W metal halide light. It can be concluded that Fe(III)-citrate complexes are important sources of ·OH radicals for some atmospheric and surface waters. Recommendations and Outlook It is believed that the photolysis of Fe(III)-citrate complexes in the presence of oxygen play an important role in producing ·OH both in atmospheric waters and surface water where high concentrations of ferric ions and citrate ions exist. The photoproduction of ·OH has a high oxidizing potential for the degradation of a wide variety of natural and anthropogenic organic and inorganic substances. We can use this method for toxic organic pollutants such as organic dyes and pesticides.     

Degradation of polychlorinated dibenzo-p-dioxins in aqueous solution by Fe(II)/H2O2/UV system

The photodegradation of polychlorinated dibenzo-p-dioxins (PCDDs), which include tetra- to octa-CDDs (TeCDD, PeCDD, HxCDD, HpCDD and OCDD), was carried out in the presence of Fe(II) and H2O2 mixed reagent. The degradation efficiency was strongly influenced by UV irradiation, and the initial concentrations of H2O2 and Fe(II). An initial TeCDD concentration of 10 ng l(-1) was completely degraded within 20 min under the optimum conditions. All PCDDs tested were successfully degraded by Fe(II)/H2O2/UV treatment and complete degradation of TeCDD, PeCDD and HxCDD was achieved within 120 min. PCDD photodegradation rates decreased with the number of chlorine atoms. The degradation process of TeCDD by this system seems to be initiated by an oxidative reaction (OH* radical attack) because less chlorinated DDs as intermediate products were not detected. From the Frontier electron density calculation, the first OH* radical attack positions on TeCDD were found to be four C atoms neighboring two O atoms. The decomposition of TeCDD gave 4,5-dichlorocatechol as an intermediate product. A TeCDD degradation scheme was proposed based on the identified intermediate and the values of Frontier electron density. Based on these results, Fe(II)/H2O2/UV system could be useful technology for the treatment of wastewater containing persistent pollutants such as dioxins and polychlorinated biphenyls.     

Oxidation of MCPA and 2,4-D by UV radiation, ozone, and the combinations UV/H2O2 and O3/H2O2

The phenoxyalkyl acid derivative herbicides MCPA (4-chloro 2-methylphenoxyacetic acid) and 2,4-D (2,4-dichlorophenoxyacetic acid) were oxidized in ultrapure water by means of a monochromatic UV irradiation and by ozone, as well as by the combinations UV/H2O2 and O3/H2O2. In the direct photolysis of MCPA, the quantum yield at 20 degrees C was directly evaluated and a value of 0.150 mol Eins(-1) was obtained in the pH range 5-9, while a lower value of 0.41 x 10(-2) mol Eins(-1) was determined at pH=3. Similarly, for 2,4-D a value of 0.81 x 10(-2) mol Eins(-1) was deduced, independent of the pH of work. The influence of the additional presence of hydrogen peroxide was established in the combined process UV/H2O2, and the specific contribution of the radical pathway to the global photo-degradation was evaluated. The oxidation by ozone and by the combination O3/H2O2 was also studied, with the determination of the rate constants for the reactions of both herbicides with ozone and hydroxyl radicals at 20 degrees C. These rate constants for the direct reactions with ozone were 47.7 and 21.9 M(-1) s(-1) for MCPA and 2,4-D respectively, while the found values for the rate constants corresponding to the radical reactions were 6.6 x 10(9) and 5.1 x 10(9) M(-1) s(-1).     

Comparison of the degradation of p-hydroxybenzoic acid in aqueous solution by several oxidation processes

A comparative study is made of 12 methods of chemical oxidation applied to degrading p-hydroxybenzoic acid in aqueous solution. The oxidation processes tested were: UV, O3, UV/TiO2, O3/Fe2+, O3/H2O2, O3/UV, UV/H2O2, H2O2/Fe2+, H2O2/Fe2+/O3, UV/H2O2/O3, H2O2/Fe2+/UV and O3/UV/H2O2/Fe2+. The 12 processes were ranked by reactivity. In a kinetic study, the overall kinetic rate constant was split up into three components: direct oxidation by UV irradiation (photolysis), direct oxidation by ozone (ozonation), and oxidation by free radicals (mainly OH*).     

Comparative study of H(2)O(2) and O3 effects on radiation treatment of TCE and PCE

The effects of H(2)O(2) and O(3) on the decomposition of trichloroethylene (TCE) and perchloroethylene (PCE) by gamma-rays (gamma-rays) were investigated in this work. The combined gamma-rays/O(3) process showed a synergistic effect and enhanced the removal of TCE and PCE compared with gamma-rays alone, but, the gamma-rays/H(2)O(2) process did not increase the removal. This interesting result was successfully identified by an electron paramagnetic resonance spectroscopy/spin-trapping method that can quantify hydroxyl radicals, which is directly related to the efficiency of TCE and PCE decomposition. For gamma-rays/H(2)O(2) system, there was no difference of hydroxyl radical production between gamma-rays alone and gamma-rays/H(2)O(2). This indicates gamma-rays cannot activate H(2)O(2) to produce hydroxyl radicals and this causes no increase of TCE and PCE removals. To the contrary, the production of hydroxyl radicals was obviously increased in the case of gamma-rays/O(3) process. This suggests additional hydroxyl radicals are produced from the reaction of O(3) with the irradiation products of water such as hydrated electrons, hydrogen atoms, etc. and this accelerates the removal of TCE and PCE.     

2-Chlorophenol induced hydroxyl radical production in mitochondria in Carassius auratus and oxidative stress--an electron paramagnetic resonance study

In our previous study, electron paramagnetic resonance (EPR) evidence of reactive oxygen species (ROS) production in Carassius auratus following 2-chlorophenol (2-CP) administration was provided. To further investigate the potential pathway of ROS production, liver mitochondria of C. auratus was isolated and incubated with 2-CP for 30 min. An EPR analysis indicated ROS was produced, and intensities of ROS increased with increasing concentrations of 2-CP. The ROS was then assigned OH by comparing with Fenton reaction. Either catalase or superoxide dismutase, extinguished OH completely in the mitochondria mixture. These facts suggested that O2(.-) and H2O2 contributed to the formation of OH in mitochondria in C. auratus stressed by 2-CP. Combining previous references and our own data, it is reasonable to suggest that 2-CP is first oxidized by H2O2 present in vivo to form phenoxyl radical under the catalytic action of cellular peroxidase (1); phenoxyl radical oxidizes mitochondria NADH to NAD in the presence of NADH (2); NAD reacts with oxygen in vivo to produce O2(.-) (3); O2(.-) is spontaneously dismutated by SOD to form H2O2 and O2, which creates a renewable supply of H2O2 as the initiators of the chain reactions until NADH is consumed (4); simultaneously with reaction (4), O2(.-) reacts with H2O2 to form OH radical via the Haber-Weiss reaction (5). A strong negative correlation (r=-0.9278, p<0.01) between glutathione (GSH) pool and OH production was observed after fish were i.p. injected with 2-CP (250 mg kg(-1)), indicating the depletion of GSH caused by OH.     

Photochemical degradation of 1,3-dinitrobenzene in aqueous solution in the presence of hydrogen peroxide

A study on the destruction of 1,3-dinitrobenzene (1,3-DNB) in aqueous solution was carried out under ultraviolet (UV) irradiation alone and UV irradiation in the presence of hydrogen peroxide (H2O2). The combination of UV and H2O2 is significantly effective in degrading 1,3-DNB in terms of initial reaction rate and the mineralization of organic carbons. The photodegradation process can be influenced in certain extent by increasing the content of H2O2 and the acidity of reaction matrices. It was found that a variety of phenolic intermediates and inorganic acid were formed via hydroxyl radicals attacking the parent compound. The UV/H2O2 oxidation of 1,3-DNB was characterized by pseudo-zero order reaction for the degradation of 1,3-DNB with a 20 times enhanced rate constant of 1.36 x 10(-7) Ms(-1) and the initial rate constant was dependent on the initial concentration of 1,3-DNB.     

Fe<Superscript>0</Superscript>-based system as innovative technology for degrading trichloromethane: Redox removal characteristics

BACKGROUND: The spent waste of aliphatic chlorinated solvents has caused severe deterioration of groundwater quality. Trichloromethane (TCM), which shows health and toxicological effects on human beings, was selected as a model compound to be dechlorinated through a redox system. METHODS: The Fe0-based system including Fe0/H2O, Fe0/UV, Fe0/H2O2, and Fe0/UV/H2O2 was explored to evaluate its performance in dechlorinating TCM. H2O2 was dosed at later reaction time points to initiate Fenton or photo-Fenton reactions. The first two systems demonstrate the reductive dechlorination of TCM by Fe0-released electrons, while the latter two show dechlorination of TCM by both electron reduction and hydroxyl radical oxidation. The system parameters of TCM remaining, Cl- buildup, Fe2+ accumulation, H2O2 residue, and ORP were measured to describe different redox characteristics of TCM dechlorination. The Cl- buildup was used as a way to describe the degree of TCM dechlorination in an open reaction system. RESULTS: Reductive dechlorination efficiencies of TCM were 5% and 6% for the systems of Fe0/H2O and Fe0/UV, respectively. In contrast, the Fe/H2O2 and Fe0/UV/H2O2 systems were capable of dechlorinating TCM reductively and oxidatively by 14% and 15%, respectively. The presence of UV light was found to retard the dissolution of Fe2+, but it enhanced the rate of chloride buildup, based on the comparison of Fe0/H2O and Fe0/UV systems. In addition, WV irradiation plays only a minor role in the Fe0/UV/H2O2 system, in view of TCM dechlorination. Application of small amount of H2O2 results in the increase of Fe2+ accumulation rate in the Fe0/H2O2 system. CONCLUSIONS: TCM was dechlorinated mostly through post Fenton oxidation; reductive reaction represents a less efficient way to dechlorinate TCM. The efficiencies of overall TCM dechlorination for the two systems of Fe0/H2O2 and Fe0/UV/ H2O2 are comparable to each other, and this implies that the presence of UV irradiation imposes no significant enhancement. RECOMMENDATIONS AND OUTLOOKS: It is highly recommended to initiate effective redox dechlorination of TCM with the system of Fe0/H2O2, where the H2O2 in excess is applied at a later reaction time point.     

Kinetic and chemical assessment of the UV/H2O2 treatment of antiepileptic drug carbamazepine

The UV/H2O2-induced degradation of carbamazepine, a worldwide used antiepileptic drug, recently found as contaminant in many municipal sewage treatment plant (STP) effluents and other aquatic environments, is investigated. The oxidation treatment caused an effective removal of the drug. At complete abatement of the substrate after 4 min treatment, a 35% value of removed total organic carbon (TOC) was obtained. A kinetic constant of (2.05+/-0.14) x 10(9) lmol(-1)s(-1) was determined for OH radical attack to carbamazepine in the UV/H2O2 process. Preparative TLC of the reaction mixture led to the isolation of acridine-9-carboxaldehyde as a reaction intermediate. HPLC and GC/MS analysis indicated formation of small amounts of acridine, salicylic acid, catechol and anthranilic acid among the reaction products. Under the same reaction conditions, synthetically prepared 10,11-epoxycarbamazepine was easily degraded to acridine as main product, suggesting that this epoxide is a likely intermediate in the oxidative conversion of carbamazepine to acridine. Under sunlight irradiation, carbamazepine in water underwent slow degradation to afford likewise acridine as main product. In view of the mutagenic properties of acridine, these results would raise important issues concerning the possible environmental impact of carbamazepine release through domestic wastewaters and support the importance of prolonged oxidation treatments to ensure complete degradation of aromatic intermediates.     

Determination of quantum yields for the photolysis of Fe(III)-hydroxo complexes in aqueous solution using a novel kinetic method

The determination of quantum yields for the photolysis of Fe(III)-hydroxo complexes is important for the quantitative investigation of hydroxyl radical (*OH) production, not only in a natural water body, but also in the photo-Fenton process. A novel kinetic method, using a *OH probe compound, was established for the determination of the quantum yields in this study. The method was based on measuring the pseudo-first-order rate constant of the photodecomposition of dimethylsulfoxide (DMSO) in which DMSO and its primary products scavenged the *OH at an identical rate. The preliminary experiments for the photodecomposition kinetics supported the suitability of DMSOs as a probe compound for determining quantum yields. The individual quantum yields for the photolysis of the monomeric Fe(III) complexes, in the wavelength range 240-380 nm, were determined by the photodecomposition kinetics of the hydroxyl radical (*OH) probe compound (DMSO). The determined values of the individual quantum yields were 0.046+/-0.00052 for Fe3+ (H2O)6 (hexaaquo ion) and 0.69+/-0.025 for Fe(OH)2+ (H2O)5 (hydroxypentaaquo ion) at 254 nm, and showed decreasing values with increasing wavelength, in the ranges of 240-380 nm. The quantum yields between 240 and 280 nm were newly reported in this study, and the values obtained between 280 and 380 nm were in good agreement with the literature values.     

Investigation of the generation of hydroxyl radicals and their oxidative role in the presence of heterogeneous copper catalysts

The presence and impact of hydroxyl radicals generated via the catalytic decomposition of H(2)O(2) over heterogeneous copper catalysts were investigated by using two detection methods, an electron spin resonance-spin trapping method and a chemical probe method. Detection of the (5,5-dimethyl-1-pyrroline-N-oxide)-OH adduct signal and formation of 4-chlorocatechol during the oxidation of a 4-chlorophenol substrate demonstrated that the three heterogeneous copper catalysts employed here (CuO, Cu/Al(2)O(3) and CuO.ZnO/Al(2)O(3)) were capable of generating hydroxyl radicals in combination with H(2)O(2). The oxidative mechanism of the hydroxyl radical in the presence of heterogeneous copper catalysts is discussed with regard to the further oxidation of the (5,5-dimethyl-1-pyrroline-N-oxide)-OH adduct and hydroxylated products of 4-chlorophenol oxidation. Interestingly, integration of the 5,5-dimethyl-1-pyrroline-N-oxide-OH adduct signal could not be used to reliably measure the total amount of hydroxyl radicals generated as a result of oxidative attack on the adduct. This may be as a result of locally higher hydroxyl radical concentrations in the presence of a heterogeneous catalyst leading to further unwanted oxidation of the (5,5-dimethyl-1-pyrroline-N-oxide)-OH.