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).     

The role of organic ligands in ferrous-induced photochemical degradation of 2,4-dichlorophenoxyacetic acid

Recent studies have shown that hydrogen peroxide is generated in a ferrioxalate-induced photoreductive reaction, but information about the effect of organic ligands on the photochemical behaviour of ferrous species is limited. The degradation of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) by a ferrous-catalyzed oxidation in the presence of various ligands such as formate, citrate, malelate, oxalate, and ethylenediaminetetra-acetic acid (EDTA) was studied. The experiments were conducted under either dark or irradiated (350n m) conditions. Forty-two percent and 34% of 2,4-D were removed by the Fe(2+)/oxalate/UV and Fe(2+)/citrate/UV processes, respectively, after 30 min of reaction and oxidative intermediates were obtained in both cases. The presence of hydroxylated intermediates suggests that 2,4-D may be attacked by hydroxyl radicals, which are the products of the photo-Fenton-like reaction. As such, hydrogen peroxide was produced by the photolysis of ferrous oxalate or ferrous citrate, referred to hereafter as photogenerated H(2)O(2). As expected, the total removal percentage of 2,4-D jumped to 97% when 1mM of hydrogen peroxide (so-called spiked H(2)O(2)) was externally added to the reaction vessel to initiate the Fe(2+)/oxalate/UV process. Therefore, the treatment of 2,4-D by the Fe(2+)/oxalate/H(2)O(2)/UV system can be operated in two steps: the photolysis of ferrous oxalate first, followed by adding the spiked H(2)O(2) sometime after the commencement of the reaction. A two-phase model has been developed to describe this tandem ferrous-catalyzed photooxidation, which would help to achieve the mineralization of 2,4-D.     

Kinetics of simazine advanced oxidation in water

Comparison of the effects and kinetics of UV photolysis and four advanced oxidation systems (ozone, ozone/hydrogen peroxide, ozone/UV radiation and UV radiation/hydrogen peroxide) for the removal of simazine from water has been investigated. At the conditions applied, the order of reactivity was ozone < ozone/hydrogen peroxide < UV radiation < ozone/UV radiation and UV radiation/hydrogen peroxide. Rate constants of the reactions between ozone and simazine and hydroxyl radical and simazine were found to be 8.7 M-1s-1 and 2.1 x 10(9) M-1s-1, respectively. Also, a quantum yield of 0.06 mol.photon-1 was found for simazine at 254 nm UV radiation. The high value of the quantum yield corroborated the importance of the direct photolysis process. Percentage contributions of direct reaction with ozone, reaction with hydroxyl radicals and direct photolysis were also quantified.     

Light regime, riboflavin, and pH effects on 2,4-D photodegradation in water

A laboratory study was conducted to determine the effects of light regime, riboflavin, and pH on photodegradation of 2,4-D in aqueous solution. In controlled-environment chamber experiments, riboflavin sensitized 2,4-D photolysis in a concentration-dependent manner under both attenuated UV (-UV) and enhanced UV (+UV) light regimes. The photolysis half-life of 2,4-D in solutions containing 10 mg L-1 riboflavin was 9.7 and 12.5 h when exposed to +UV and -UV, respectively, compared to no photolysis in the absence of riboflavin. In contrast, the extrapolated half-life of 2,4-D in solutions containing 2.5 mg L-1 riboflavin was 46 h under +UV and 72 h under -UV. The rate of 2,4-D photolysis in the presence of riboflavin increased under both light regimes as initial pH of the solution was decreased from 7.5 to 4.5. The half-life of 2,4-D in the presence of 10 mg L-1 riboflavin at pH 4.5 and exposed to +UV was 1.6 h. Lumichrome, a principal photoproduct of riboflavin, did not photosensitize 2,4-D. Concentrations of 2,4-dichlorophenol formed as a result of riboflavin-sensitized 2,4-D photolysis were higher under the -UV than the +UV regime. These results indicate that riboflavin concentration, solution pH, and light regime are interacting factors that may be manipulated to enhance rates of aqueous 2,4-D photolysis.     

Degradation of the pharmaceutical metronidazole via UV, Fenton and photo-Fenton processes

Degradation rates and removal efficiencies of Metronidazole using UV, UV/H2O2, H2O2/Fe2+, and UV/H2O2/Fe2+ were studied in de-ionized water. The four different oxidation processes were compared for the removal kinetics of the antimicrobial pharmaceutical Metronidazole. It was found that the degradation of Metronidazole by UV and UV/H2O2 exhibited pseudo-first order reaction kinetics. By applying H2O2/Fe2+, and UV/H2O2/Fe2+ the degradation kinetics followed a second order behavior. The quantum yields for direct photolysis, measured at 254 nm and 200-400 nm, were 0.0033 and 0.0080 mol E(-1), respectively. Increasing the concentrations of hydrogen peroxide promoted the oxidation rate by UV/ H2O2. Adding more ferrous ions enhanced the oxidation rate for the H2O2/Fe2+ and UV/H2O2/Fe2+ processes. The major advantages and disadvantages of each process and the complexity of comparing the various advanced oxidation processes on an equal basis are discussed.     

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.     

High temperature dependence of 2,4-dichlorophenoxyacetic acid degradation by Fe3+/H(2)O(2) system

This study demonstrates the importance of reaction temperature on the degradation of 2,4-dichlorophenoxyacetic acid (2,4-D). In addition, we provide a mechanistic explanation for the temperature dependence of 2,4-D degradation. Thermal enhancement of 2,4-D degradation and H(2)O(2) decomposition was measured in the absence and in the presence of the z.rad;OH scavenger (t-butanol). The half-life for 2,4-D degradation was reduced by more than 70-fold in the absence of t-butanol, and by more than 700-fold, in the presence of t-butanol, when the reaction temperature was increased from 10 to 50 degrees C. In addition, similar temperature relationships were found for H(2)O(2) decomposition. The major reason for the high temperature dependence of the Fe(3+)/H(2)O(2) system in the case of 2,4-D degradation is due to the dependence of the initiation reaction of the Fe(3+)/H(2)O(2) system (i.e., Fe(3+)+H(2)O(2)-->Fe(2+)+HO(2)(z.rad;)+H(+) upon temperature), which is entirely consistent with the kinetics of the activation energy. In the presence of a z.rad;OH scavenger, the initiation reaction of the Fe(3+)/H(2)O(2) system became a determining factor of this temperature dependence, whereas in the absence of z.rad;OH scavenger, several other radical reactions played a role and this result in an apparent decrease in the activation energy for 2,4-D degradation. Moreover, the enhanced 2,4-D removal at higher temperatures did not alter H(2)O(2) utilization. The practical implications of the thermal enhancement of the Fe(3+)/H(2)O(2) system are discussed.     

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.     

Kinetics of simazine advanced oxidation in water

Abstract

Comparison of the effects and kinetics of UV photolysis and four advanced oxidation systems (ozone, ozone/hydrogen peroxide, ozone/UV radiation and UV radiation/hydrogen peroxide) for the removal of simazine from water has been investigated. At the conditions applied, the order of reactivity was ozone < ozone/hydrogen peroxide < UV radiation < ozone/UV radiation and UV radiation/hydrogen peroxide. Rate constants of the reactions between ozone and simazine and hydroxyl radical and simazine were found to be 8.7 M^‐1s^‐1 and 2.1x10⁹ M^‐1s^‐1, respectively. Also, a quantum yield of 0.06 mol.photon^‐1 was found for simazine at 254 nm UV radiation. The high value of the quantum yield corroborated the importance of the direct photolysis process. Percentage contributions of direct reaction with ozone, reaction with hydroxyl radicals and direct photolysis were also quantified.     

Quantum yield study of the photodegradation of hydrophobic dyes in the presence of acetone sensitizer.

The photodegradation of hydrophobic disperse dyes with different chromophores in the presence of acetone (ACE) was investigated. In this study, the photodecay of dyes was carried out in the Rayonet RPR-200 merry-go-round photoreactor, with 253.7 nm monochromatic ultraviolet (UV) lamps. A typical azo disperse dye (CI disperse yellow 7--DY7) and an anthraquinone disperse dye (CI disperse orange--DO11) were used as the probe compounds. The results demonstrate that the addition of acetone increases the solubility of hydrophobic disperse dyes and enhances the photosensitization reaction simultaneously. More than ten times of quantum yield enhancement is observed in the presence of ACE photosensitizer than in water alone. The photodegradation of DY7 and DO11 is dominated by photoreduction, which follows pseudo first-order decay, and the rate constants strongly depend on the solvent system (i.e., ACE/H2O ratios) and the initial pH levels. The decay quantum yields of dyes are normally observed with the increase of the ACE/H2O ratio. The optimum quantum yields of DY7 and DO11 were determined at 0.5 (v/v) and 0.25 (v/v), respectively, in alkaline conditions. A further increase in the ACE/H2O ratio reduces the quantum yields, possibly due to light attenuation by excess acetone.     

Fresnel lens to concentrate solar energy for the photocatalytic decoloration and mineralization of orange II in aqueous solution

The decoloration and mineralization of the azo dye orange II under conditions of artificial ultraviolet light and solar energy concentrated by a Fresnel lens in the presence of hydrogen peroxide and TiO(2)-P25 was studied. A comparative study to demonstrate the viability of this solar installation was done to establish if the concentration reached in the focus of the Fresnel lens was enough to improve the photocatalytic degradation reaction. The degradation efficiency was higher when the photolysis was carried out under concentrated solar energy irradiation as compared to UV light source in the presence of an electron acceptor such us H(2)O(2) and the catalyst TiO(2). The effect of hydrogen peroxide, pH and catalyst concentration was also determined. The increase of H(2)O(2) concentration until a critical value (14.7 mM) increased both the solar and artificial UV oxidation reaction rate by generating hydroxyl radicals and inhibiting the (e(-)/h(+)) pair recombination, but the excess of hydrogen peroxide decreases the oxidation rate acting as a radical or hole scavenger and reacting with TiO(2) to form peroxo-compounds, contributing to the inhibition of the reaction. The use of the response surface methodology allowed to fit the optimal values of the parameters pH and catalyst concentration leading to the total solar degradation of orange II. The optimal pH range was 4.5-5.5 close to the zero point charge of TiO(2) depending on surface charge of catalyst and dye ionization state. Dosage of catalyst higher than 1.1 gl(-1) decreases the degradation efficiency due to a decrease of light penetration.     

Photodegradation of humic acids in the presence of hydrogen peroxide

A batch photoreactor was used to evaluate the UV/H2O2 oxidation process for the removal of humic acids in water. A 450-W UV lamp with high-pressure mercury vapor was employed as the light source. The residues of humic acids and hydrogen peroxide were measured for assessment of process performance and understanding of process reaction behavior. The UV photolysis alone can play an important role in the degradation of humic acids. The presence of hydrogen peroxide was found to promote the degradation efficiency. However, excessive dosage of H2O2 does not further improve the degradation of humic acids. On the contrary, the lower the H2O2 dosage the higher the amount of humic acids which can be removed. Aeration with air does not favor the removal efficiency of humic acids as the oxidation lasts for a sufficiently long time. The presence of carbonate species deteriorates the humic acids' removal, whereas it results in a larger amount of H2O2 decomposition.     

Atrazine removal by ozonation processes in surface waters

Atrazine (6-chloro-N-ethyl-N'-isopropyl-1,3,5-triazinedyl-2,4-diamine) was treated with ozone alone and in combination with hydrogen peroxide or UV radiation in three surface waters. Experiments were carried out in two bubble reactors operated continuously. Variables investigated were the ozone partial pressure, temperature, pH, mass flow ratio of oxidants fed: hydrogen peroxide and ozone and the type of oxidation including UV radiation alone. Residence time for the aqueous phase was kept at 10 min. Concentrations of some intermediates, including deethylatrazine, deisopropylatrazine and deethyldeisopropylatrazine, were also followed. The nature of water, specifically the alkalinity and pH were found to be important variables that affected atrazine (ATZ) removal. Surface waters with low alkalinity and high pH allowed the highest removal of ATZ to be reached. There was an optimum hydrogen peroxide to ozone mass flow ratio that resulted in the highest ATZ removal in each surface water treated. This optimum was above the theoretical stoichiometry of the process. Therefore, to reach the maximum removal of ATZ in a O3/H2O2 process, more hydrogen peroxide was needed in the surface waters treated than in ultrapure water under similar experimental conditions. In some cases, UV radiation alone resulted in the removal of ATZ higher than ozonation alone. This was likely due to the alkalinity of the surface water. Ozonation and UV radiation processes yield different amounts of hydrogen peroxide. Combined ozonations (O3/H2O2 and O3/UV) lead to ATZ removals higher than single ozonation or UV radiation but the formation of intermediates was higher.     

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.     

Influence of various reaction parameters on 2,4-D removal in photo/ferrioxalate/H(2)O(2) process

The influence of various reaction parameters on herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) removal were examined in the photo/ferrioxalate/H(2)O(2) system, with regard to: (1) sulfate, phosphate, and z.rad;OH scavenger, as solution constituent; and (2) light intensity, ferrioxalate, H(2)O(2), and oxalate concentration, as operating parameter. In terms of 2,4-D removal, the photo/ferrioxalate/H(2)O(2) system has always been superior to the photo/Ferric ion/H(2)O(2) system, despite the high presence of anions (sulfate 100 mM, phosphate 1 mM) or z.rad;OH scavenger. Not only the rate of 2,4-D removal, but also the decomposition rate of H(2)O(2) and oxalate proportionally increase with light intensity. The ferrioxalate concentration determines the light absorption fraction, and thus, controls the rates of 2,4-D removal, and the decomposition of H(2)O(2) and oxalate, are predicted from kinetic formulations. The optimal concentration of H(2)O(2) and oxalate, according to the extent of the z.rad;OH scavenging reaction with these reagents, has been demonstrated for 2,4-D removal. It was found that an increasing oxalate concentration, which bears the burden of increased dissolved organic carbon (DOC), does not occur. This is because its decomposition, as a result of the photochemical reduction of the ferric oxalate complex, results in a decrease of the equivalent DOC. The importance of the key reaction factors to be considered, when applying this system to real wastewater treatment, is also discussed.     

Photooxidative removal of the herbicide Acid Blue 9 in the presence of hydrogen peroxide: modeling of the reaction for evaluation of electrical energy per order (E EO)

The present work deals with photooxidative removal of the herbicide, Acid Blue 9 (AB9), in water in the presence of hydrogen peroxide (H2O2) under UV light illumination (30 W). The influence of the basic operational parameters such as amount of H2O2, irradiation time and initial concentration of AB9 on the photodegradation efficiency of the herbicide was investigated. The degradation rate of AB9 was not appreciably high when the photolysis was carried out in the absence of H2O2 and it was negligible in the absence of UV light. The photooxidative removal of the herbicide was found to follow pseudo-first-order kinetic, and hence the figure-of-merit electrical energy per order (E Eo) was considered appropriate for estimating the electrical energy efficiency. A mathematical relation between the apparent reaction rate constant and H2O2 used was applied for prediction of the electricity consumption in the photooxidative removal of AB9. The results indicated that this kinetic model, based on the initial rates of degradation, provided good prediction of the E Eo values for a variety of conditions. The results also indicated that the UV/H2O2 process was appropriate as the effective treatment method for removal of AB9 from the contaminated wastewater.     

A tubular ceramic membrane coated with TiO2-P25 for radial addition of H2O2 towards AMX removal from synthetic solutions and secondary urban wastewater

Environmental Science and Pollution Research - This work aims to integrate several hydrogen peroxide (H2O2) activation mechanisms, photolysis (UVC irradiation), chemical electron transfer (TiO2-P25...     

The direct photolysis and photocatalytic degradation of alachlor at different TiO2 and UV sources

Direct photolysis and photocatalytic degradations of alachlor, a widely used herbicide, were studied using three different monochromatic UV lamps (254, 300 and 350 nm) and two TiO(2) sources. Both the direct photolysis and photocatalytic degradations of alachlor follow pseudo-first-order decay kinetics. TiO(2)-P25 was found to be an effective photocatalyst compared to TiO(2)-BDH. The direct photolysis of alachlor was dominant at 254 nm even if TiO(2) was present in the solution. Among the three UV wavelengths used, the highest photocatalysis quantum yield was obtained at 300 nm. The photocatalytic degradation rate of alachlor increased with the dosages of TiO(2), but an overdose of TiO(2) would retard the reaction due to light attenuation. Photocatalytic reactions were slightly enhanced in an alkaline medium, and the different proton sources causing various degrees of rate retardation were due to the presence of the corresponding counter anions. This effect was diminished at a later stage after the reaction intermediates were formed.     

O3/H2O2法去除浮选药剂丁基黄药

采用O3/H2O2法去除水中丁基黄药,考察了H2O2/O3摩尔比、pH值、丁基黄药初始浓度、温度和自由基抑制剂对丁基黄药的去除效果的影响。结果表明,在相同O3投加量下,H2O2量越大,丁基黄药去除率越高。pH值为7～9,温度在293～303 K的范围内,O3/H2O2对丁基黄药都有很高的去除率。碳酸氢根和叔丁醇能在一定程度上降低丁基黄药的降解效率。研究还发现,在O3和H2O2投加量相同的条件下,H2O2多次投加对水中丁基黄药的处理效果明显优于一次性投加。GC/MS分析表明,O3/H2O2氧化丁基黄药氧化产物为羧酸类物质。     

Mechanism and kinetic model for the decolorization of the azo dye Reactive Black 5 by hydrogen peroxide and UV radiation

A kinetic model for the decolorization of C.I. Reactive Black 5 by the combination of hydrogen peroxide and UV radiation was developed based on experimental results and known chemical and photochemical reactions. The observed kinetic reaction coefficient was determined and correlated as a function of hydrogen peroxide concentration and UV intensity. The validity of the rate expression was tested experimentally in a parameterization study. The decolorization rate follows pseudo-first order kinetics with respect to dye concentration. The rate increases linearly with UV intensity and nonlinearly with increasing hydrogen peroxide concentration, going from a linear relationship at low H(2)O(2) concentrations to a maximum as hydrogen peroxide concentration continues to increase. The decolorization rate expression derived from the proposed reaction mechanism was reconciled with that used for correlating the experimental data.