Abiotic Fe(III) induced mineralization of phenolic substances

The redox process between iron(III) (in dissolved form and as the mineral phase ferrihydrite) and phenolic substances has been examined. We investigated the relationship between the structure and reactivity for the dihydrobenzene reductants catechol, hydroquinone and resorcine, and for the 2-methoxyphenol guaiacol with iron(III), by determining the rate of the Fe(III) reduction as well as the production of CO2. This work demonstrates that catechol and guaiacol will be effectively oxidized to CO2 by reducing iron(III). Hydroquinone shows a reduction of iron(III), but no accompanying mineralization could be determined. In contrast, resorcine showed no reaction with Fe(II). The deciding factor on whether or not mineralization occurs were controlled by the position of the hydroxy groups. It is shown that phenolic substances with two hydroxy groups in the orthoposition or at least one hydroxy group and a methoxy group can be oxidized to CO2 while iron(III) is reduced.     

Degradation of anti-inflammatory drug ketoprofen by electro-oxidation: comparison of electro-Fenton and anodic oxidation processes

The electrochemical degradation of the nonsteroidal anti-inflammatory drug ketoprofen in tap water has been studied using electro-Fenton (EF) and anodic oxidation (AO) processes with platinium (Pt) and boron-doped diamond (BDD) anodes and carbon felt cathode. Fast degradation of the parent drug molecule and its degradation intermediates leading to complete mineralization was achieved by BDD/carbon felt, Pt/carbon felt, and AO with BDD anode. The obtained results showed that oxidative degradation rate of ketoprofen and mineralization of its aqueous solution increased by increasing applied current. Degradation kinetics fitted well to a pseudo-first-order reaction. Absolute rate constant of the oxidation of ketoprofen by electrochemically generated hydroxyl radicals was determined to be (2.8?±?0.1)?×?10⁹ M^?1 s^?1 by using competition kinetic method. Several reaction intermediates such as 3-hydroxybenzoic acid, pyrogallol, catechol, benzophenone, benzoic acid, and hydroquinone were identified by high-performance liquid chromatography (HPLC) analyses. The formation, identification, and evolution of short-chain aliphatic carboxylic acids like formic, acetic, oxalic, glycolic, and glyoxylic acids were monitored with ion exclusion chromatography. Based on the identified aromatic/cyclic intermediates and carboxylic acids as end products before mineralization, a plausible mineralization pathway was proposed. The evolution of the toxicity during treatments was also monitored using Microtox method, showing a faster detoxification with higher applied current values.     

Hydrogen peroxide mediated photodegradation of phenol as studied by a flash photolysis/HPLC technique

The technique of flash photolysis followed by high-performance liquid chromatography has been applied to the study of the photodegradation of phenol (I) in the presence of hydrogen peroxide. Progress of the reaction of I (0.1 mM) in undegassed aqueous solution ([H2O2]/[I] = 200/l) was observed by using multiple flashes (16 J). Analysis after a single flash indicated that catechol and hydroquinone were the primary products of the reaction. The reaction was found to be independent of pH in the range 7.0-9.0, but the yield of degradation decreased at pH > 9.0 and at pH < 7.0. The effects of the hydrogen peroxide concentration and flash energy on the chemical yield of the pollutant degradation, and product formation, were investigated as well. The mechanism of the reaction is discussed. A possibility of the application of flashlamps as powerful sources of the UV irradiation in industrial reactors for wastewater treatment is suggested.     

Mechanisms of product formation from the pyrolytic thermal degradation of catechol

Catechol has been identified as one of the most abundant organic products in tobacco smoke and a major molecular precursor for semiquinone type radicals in the combustion of biomass material. The high-temperature gas-phase pyrolysis of catechol under hydrogen-rich and hydrogen-lean conditions was studied using a fused-silica tubular flow reactor coupled to an in-line GC/MS analytical system. Thermal degradation of catechol over temperature range of 250-1000 degrees C with a reaction time of 2.0s yielded a variety products including phenol, benzene, dibenzofuran, dibenzo-p-dioxin, phenylethyne, styrene, indene, anthracene, naphthalene, and biphenylene. Ortho-benzoquinone which is typically associated with the presence of semiquinone radicals was not observed and is proposed to be the result of fast decomposition reactions that lead to a variety of other reaction products. This is in contrast to the decomposition of hydroquinone that produced para-benzoquinone as the major product. A detailed mechanism of the degradation pathway of catechol is proposed.     

负载TiO2/Fe3+的玻璃纤维反应器光催化苯酚

以玻璃纤维为载体,将TiO2负载到其表面形成了空间玻璃纤维反应器,引入Fe3+作为掺杂改性离子,形成了负载TiO2/Fe3+的空间玻璃纤维光催化反应器,并以高压汞灯为光源进行了光催化降解水中苯酚的实验研究,考察了影响苯酚光催化降解的因素,确定了在UV365～250 W光源照射下,pH为3～5,O2通入量1.0 L/(min.L),反应器内上升流速为0.7 m/min等实验条件下,初始浓度为30 mg/L的苯酚废水经120 min光催化反应后,降解率可达到85%,矿化率可达80%。     

Degradation of some biorecalcitrant pesticides by homogeneous and heterogeneous photocatalytic ozonation

Photo-Fenton/ozone (PhFO) and TiO2-photocatalysis/ozone (PhCO) coupled systems are used as advanced oxidation processes for the degradation of the following biorecalcitrant pesticides: alachlor, atrazine, chlorfenvinfos, diuron, isoproturon and pentachlorophenol. These organic compounds are considered Priority Hazardous Substances by the Water Framework Directive of the European Commission. The degradation process of the different pesticides, that occurs through oxidation of the organic molecules by means of their reaction with generated OH radical, follows a first and zero-order kinetics, when PhFO and PhCO are applied, respectively. These two Advanced Oxidation Processes, together with the traditional ozone+UV, have been used to investigate TOC reduction of the different pesticide aqueous solutions. The best results of pesticide mineralization are obtained when PhFO is applied; with the use of this advanced oxidation process the aqueous pesticide solutions become detoxyfied except in the case of atrazine and alachlor aqueous solutions for which no detoxification is achieved at the experimental conditions used in the work, at least after 2 and 3 h of treatment, respectively.     

Removal of propham from water by using electro-Fenton technology: kinetics and mechanism

The removal of a carbamate herbicide, propham, from aqueous solution has been carried out by the electro-Fenton process. Hydroxyl radical, a strong oxidizing agent, was generated catalytically and used for the oxidation of propham aqueous solutions. The degradation kinetics of propham evidenced a pseudo-first order degradation. The absolute rate constant of second order reaction kinetics between propham and ()OH was determined as (2.2+/-0.10)x10(9)m(-1)s(-1). The mineralization of propham was followed by the organic carbon (TOC) removal. The optimal Fe(3+) concentration was found as 0.5mM at 300mA. The 94% of initial TOC of 0.25mM propham solution was removed in 8h at the optimal conditions by using the cathode area to solution volume ratio of 3.33dm(-1). The maximum mineralization current efficiency values were obtained at 60mA in the presence of 0.5mM Fe(3+). During the electro-Fenton treatment, several degradation products were formed. These intermediates were identified by using high performance liquid chromatography, liquid chromatography-mass spectrometry, gas chromatography-mass spectrometry and ion chromatography analysis. The identified by-products allowed proposing a pathway for the propham mineralization.     

Comparative study of the oxidation of atrazine and acetone by H2O2/UV, Fe(III)/UV, Fe(iii)/H2O2/UV and Fe(II) or Fe(III)/H2O2

In this study, the rates of degradation of organic compounds by several AOPs (H₂O₂/UV, Fe(III)/UV, Fe(III)/H₂O₂/UV, Fe(II)/H₂O₂ and Fe(III)/H₂O₂) have been compared. Experiments were carried out at pH ≈ 3 (perchloric acid / sodium perchlorate solutions) and with UV reactors equipped with a low-pressure mercury vapour lamp (emission at 253.7 run). The data obtained with atrazine ([Atrazine]_o = 100 μg/L) showed that the rate of degradation of atrazine in very dilute aqueous solution is much more rapid with Fe(III)/UV than with H₂O₂/UV. Photo-Fenton process (Fe(III)/H₂O₂/UV) was found to be more efficient than H₂O₂/UV and Fe(II)/H₂O₂ for the mineralization of acetone ([Acetone]_o = 1 mM).     

Solar activated ozonation of phenol and malic acid

The effect that sunlight has on the degradation rate of two model organic compounds, phenol and malic acid, by ozone is studied. The effect seems to be due to both direct light absorption (300-320 nm photons) by ozone, which produces the pollutant degradation, and light absorption by reaction intermediates. The presence of such a light notably improves the reactivity of ozone toward the organic species, leading to a faster and complete mineralization even at large initial total organic carbon values. The use of artificial sunlight (Xe lamp) is also explored. Finally, the simultaneous presence of sunlight and other ozone degradation catalyst like transition metal ions is studied, showing the beneficial effect of such a combination.     

Efficient removal of triphenylmethane dyes from aqueous medium by in situ electrogenerated Fenton's reagent at carbon-felt cathode

Fenton's reagent (Fe2+ +H2O2) has been electrogenerated in situ in an undivided electrolytic cell from the effective reduction of Fe3+ and O2 at carbon-felt cathode for the treatment of aqueous solutions of four triphenylmethane dyes (TPMs), namely malachite green (MG), crystal violet (CV), methyl green (MeG) and fast green FCF (FCF), at pH 3.0 and room temperature. MG has been used as a model among them to study the influence of some experimental parameters on the decay kinetics, COD removal and current efficiency. The results in such electro-Fenton system are explained in terms of the many parasitic reactions involving .OH. Higher efficiency values are obtained with rising organic content and decreasing applied current. The first stage of the mineralization process, involving aromatic by-products, leads to fast decoloration as well as quick initial COD removal that fit well to a pseudo-first-order kinetics. At prolonged electrolysis time, the mineralization rate and efficiency decrease due to the formation of hardly oxidizable compounds and the enhancement of wasting reactions. Solutions of all four TPMs are quickly degraded following a pseudo-first-order decay kinetics. The absolute rate constant (kTPM) for their reaction with .OH increases in the order MeG相似文献   

Photo-Fenton treatment of TNT contaminated soil extract solutions obtained by soil flushing with cyclodextrin

The technical feasibility and performances of coupling flushing abilities of cyclodextrin solutions for 2,4,6-trinitrotoluene (TNT) removal from contaminated soil and the ability of Photo-Fenton treatment for final disposal of soil extract solutions containing high TNT loads have been investigated at laboratory scale. Methylated-beta-cyclodextrin (MCD) has shown better ability than hydroxypropyl-beta-cyclodextrin (HPCD) to complex TNT. The MCD solution increased the aqueous concentration of TNT in soil extract effluents as much as 2.1 times the concentrations obtained during the water flush of the soil. TNT in soil extract solution has been treated by Photo-Fenton. Our results indicate that MCD has a beneficial effect on the degradation rates of TNT. This relative improvement of TNT degradation rate (1.3 time) in presence of high amounts of hydroxyl radical scavengers can be ascribed to the formation of a ternary complex (TNT-cyclodextrin-iron) which can direct hydroxyl radical reaction toward TNT. Complete mineralization of soil extraction solutions was not achieved and TNT degradation pathway has been elucidated in order to ensure that no potential toxic intermediate is left at the end of the treatment time. After successive TNT hydroxylations, oxidative opening of the TNT aromatic ring quickly occurred, leading to the accumulation of short chain carboxylic acids such as oxalic acid and formic acid.     

Influence of oxalic acid formed on the degradation of phenol by Fenton reagent

The objective of this work is to examine the influence of oxalic acid formed on the degradation of phenol by Fenton reagent. Oxalic acid formed at initial stage within 30 min significantly suppresses the reduction of ferric ion, thus terminating degradation reaction. The yield of oxalic acid is dependent on the amount of ferrous ion dosed since the minimal amount of oxalic acid is formed after the degradation reaction terminates. Mineralization of phenol by Fenton reagent stagnates after 120 min under the conditions used in this study. The reason why the mineralization stagnated can be assumed to be following two mechanisms other than the depletion of H₂O₂. In the case where a small amount of ferrous ions is dosed, the reduction of ferric ions is minimal by oxalic acid formed. In the case where a large amount of ferrous ions is dosed, the amount of degradable organic compounds is insufficient owing to preferential conversion to oxalic acid. The mineralization can be enhanced by the intermittent dosing of ferrous ions, which facilitates the suppression of oxalic acid formation during the degradation by Fenton reagent.     

Fenton-like oxidation and mineralization of phenol using synthetic Fe(II)–Fe(III) green rusts

Background, aim, and scope  

In literature, the environmental applications of green rust (GR) have mainly been pointed out through the reduction of inorganic contaminants and the reductive dechlorination of chlorinated organics. However, reactions involving GR for the oxidation and mineralization of organic pollutants remain very scantly described. In this study, the ability of three synthetic Fe(II)–Fe(III) green rusts, GR(CO₃²⁻), GR(SO₄²⁻), and GR(Cl⁻), to promote Fenton-like reaction was examined by employing phenol as a model pollutant. Unlike the traditional Fenton’s reagent (dissolved Fe(II) + H₂O₂), where the pH values have to be lowered to less than 4, the proposed reaction can effectively oxidize the organic molecules at neutral pH and could avoid the initial acidification which may be costly and destructive for the in situ remediation of contaminated groundwater and soils. The green rust reactivity towards the oxidative transformation of phenol was thoroughly evaluated by performing a large kinetic study, chemical analyses, and spectroscopic investigations.     

Photodegradation of 4-tert octylphenol in aqueous solution promoted by Fe(III)

4-Tert-octylphenol (4-t-OP), a kind of endocrine-disrupting compounds, is widely distributed in natural water surroundings but can hardly be biodegraded. The advanced oxidation processes (AOPs) have been proved to be an efficient method to degrade 4-t-OP. In this study, the photodegradation of 4-t-OP in aqueous solution promoted by Fe(III) and the photooxidation mechanism were investigated. The ferric perchlorate was added into the aqueous solution for the production of hydroxyl radical. The efficiency of mineralization was monitored by total organic carbon analyzer, and photooxidation products were determined by high-performance liquid chromatography and liquid chromatography-mass spectrometer. 4-t-OP (2.4?×?10^?5 M) in aqueous solution was completely degraded after 45 min in the presence of Fe(III) (1.2?×?10^?3 M) under UV irradiation (λ?=?365 nm). The optimal pH was 3.5. Higher Fe(III) concentration or lower initial 4-t-OP concentration led to increased photodegradation efficiency of 4-t-OP. The reaction was almost completely inhibited in the presence of 2-propanol. About 70 % mineralization of the solution was obtained after 50 h. The photooxidation product was supposed to be 4-tert-octyl catechol. 4-t-OP in aqueous solution can be degraded in the presence of Fe(III) under the solar irradiation. The photoinduced degradation is due to the reaction with hydroxyl radicals. It shows that the 4-t-OP is mineralized by the inducement of Fe(III) aquacomplexes, which exposes to solar light. Therefore, the results would provide useful information for the potential application of the AOPs to remove 4-t-OP in water surroundings.     

Comparison of fenton and photo-fenton processes for livestock wastewater treatment

In this study, the photochemical degradation of livestock wastewater was carried out by the Fenton and Photo-Fenton processes. The effects of pH, reaction time, the molar ratio of Fe(2 +)/H(2)O(2), and the Fe(2 +) dose were studied. The optimal conditions for the Fenton and Photo-Fenton processes were found to be at a pH of 4 and 5, an Fe(2 +) dose of 0.066 M and 0.01 M, a concentration of hydrogen peroxide of 0.2 M and 0.1 M, and a molar ratio (Fe(2 +)/H(2)O(2)) of 0.33 and 0.1, respectively. The optimal reaction times in the Fenton and Photo-Fenton processes were 60 min and 80 min, respectively. Under the optimal conditions of the Fenton and Photo-Fenton processes, the chemical oxygen demand (COD), color, and fecal coliform removal efficiencies were approximately 70--79, 70--85 and 96.0--99.4%, respectively.     

Mineralisation of Monuron photoinduced by Fe(III) in aqueous solution

The degradation of Monuron (3-(4-chlorophenyl)-1,1-dimethylurea) photoinduced by Fe(III) in aqueous solution has been investigated. The rate of degradation depends on the concentration of Fe(OH)2+, the most photoreactive species in terms of *OH radical formation. These *OH radicals are able to degrade Monuron until total mineralisation. The primordial role of the speciation of Fe(III)-hydroxy complex in aqueous solution, for the efficiency of the elimination of pollutant, was shown and explained in detail. The formation of Fe(II) in the irradiated solution was monitored and correlated with the total organic carbon evolution. Degradation photoproducts were identified and a mechanism of degradation is proposed.     

FeAlO_x/MMT催化Fenton反应降解高浓度苯酚废水

以蒙脱土为载体制备负载型Fe/Al复合氧化物（FeAlOx/MMT）用于催化Fenton反应降解高浓度苯酚废水。实验结果表明,活性相FeAlOx中Fe/Al摩尔比为0.22时制备所得催化剂对Fenton反应具有最佳活性,且Fe/Al复合氧化物并未嵌入蒙脱土层间。在低温和高pH条件下催化体系存在诱导期,诱导期内FeAlOx/MMT缓释出Fe离子并进而由Fe离子催化溶液中的Fenton反应。通过对非均相催化降解苯酚废水的动力学研究发现,H2O2初始浓度、溶液的pH和反应温度对COD降解效率具有显著影响。调节降解过程中的温度序列和氧化剂引入程序能够缓解高温和高双氧水浓度双重因素耦合导致的HO.自消耗。在优化的降解条件下使用理论用量的H2O2可使得1 g/L的苯酚废水中苯酚降解率达到100%,而COD的降解率则达到97%。     

Degradation of clofibric acid in acidic aqueous medium by electro-Fenton and photoelectro-Fenton

Acidic aqueous solutions of clofibric acid (2-(4-chlorophenoxy)-2-methylpropionic acid), the bioactive metabolite of various lipid-regulating drugs, have been degraded by indirect electrooxidation methods such as electro-Fenton and photoelectro-Fenton with Fe(2+) as catalyst using an undivided electrolytic cell with a Pt anode and an O(2)-diffusion cathode able to electrogenerate H(2)O(2). At pH 3.0 about 80% of mineralization is achieved with the electro-Fenton method due to the efficient production of oxidant hydroxyl radical from Fenton's reaction between Fe(2+) and H(2)O(2), but stable Fe(3+) complexes are formed. The photoelectro-Fenton method favors the photodecomposition of these species under UVA irradiation, reaching more than 96% of decontamination. The mineralization current efficiency increases with rising metabolite concentration up to saturation and with decreasing current density. The photoelectro-Fenton method is then viable for treating acidic wastewaters containing this pollutant. Comparative degradation by anodic oxidation (without Fe(2+)) yields poor decontamination. Chloride ion is released during all degradation processes. The decay kinetics of clofibric acid always follows a pseudo-first-order reaction, with a similar rate constant in electro-Fenton and photoelectro-Fenton that increases with rising current density, but decreases at greater metabolite concentration. 4-Chlorophenol, 4-chlorocatechol, 4-chlororesorcinol, hydroquinone, p-benzoquinone and 1,2,4-benzenetriol, along with carboxylic acids such as 2-hydroxyisobutyric, tartronic, maleic, fumaric, formic and oxalic, are detected as intermediates. The ultimate product is oxalic acid, which forms very stable Fe(3+)-oxalato complexes under electro-Fenton conditions. These complexes are efficiently photodecarboxylated in photoelectro-Fenton under the action of UVA light.     

负载型TiO2固定相光催化降解含酚废水的试验研究

以20W紫外灯为光源,研究了将TiO2粉末负载在硅胶颗粒上,对含酚废水进行光催化降解.由试验得出光催化反应过程中的工艺条件,在此基础上添加H2O2、Fe3+、Cu2+,反应1 h后,苯酚的降解率达95%以上.     

FeAlOx/MMT催化Fenton反应降解高浓度苯酚废水

以蒙脱土为载体制备负载型Fe/Al复合氧化物(FeAlOx/MMT)用于催化Fenton反应降解高浓度苯酚废水。实验结果表明,活性相FeAlOx中Fe/Al摩尔比为0.22时制备所得催化剂对Fenton反应具有最佳活性,且Fe/Al复合氧化物并未嵌入蒙脱土层间。在低温和高pH条件下催化体系存在诱导期,诱导期内FeAlOx/MMT缓释出Fe离子并进而由Fe离子催化溶液中的Fenton反应。通过对非均相催化降解苯酚废水的动力学研究发现,H2O2初始浓度、溶液的pH和反应温度对COD降解效率具有显著影响。调节降解过程中的温度序列和氧化剂引入程序能够缓解高温和高双氧水浓度双重因素耦合导致的HO.自消耗。在优化的降解条件下使用理论用量的H2O2可使得1 g/L的苯酚废水中苯酚降解率达到100%,而COD的降解率则达到97%。