Modeling the reaction kinetics of Fenton's process on the removal of atrazine

The degradation of pesticide, atrazine (ATZ), 2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine, by Fenton's reagent (FR) was investigated as a function of reagents' concentrations and ratios in a batch reactor. The degradation of ATZ was effectively achieved by hydroxyl radicals, which were generated in the FR process. The decay rates of ATZ and the oxidation capacities of FR were found to depend on the concentrations of hydrogen peroxide and ferrous ion. The removal kinetics of ATZ are initiated by a rapid decay and then followed by a much slower one. After an extended reaction time (5-10 min), the reactions ceased because the Fe(II) and H(2)O(2) were consumed and would be deactivated in the process. A mathematical model was successfully developed to describe the two-stage reaction kinetics by using two simple but critical parameters: the initial ATZ decay rate and the final oxidation capacity of Fenton's process. In general, higher [Fe(II)] or H(2)O(2) concentrations result in faster initial decay rate and higher oxidation capacity. However, the oxidation capacity is more sensitive to the initial [Fe(II)] due to the presence of side reactions as discussed in the paper.     

Citric acid-modified Fenton's reaction for the oxidation of chlorinated ethylenes in soil solution systems

Fenton's reagent, a solution of hydrogen peroxide and ferrous iron catalyst, is used for an in situ chemical oxidation of organic contaminants. Sulfuric acid is commonly used to create an acidic condition needed for catalytic oxidation. Fenton's reaction often involves pressure buildup and precipitation of reaction products, which can cause safety hazards and diminish efficiency. We selected citric acid, a food-grade substance, as an acidifying agent to evaluate its efficiencies for organic contaminant removal in Fenton's reaction, and examined the impacts of using citric acid on the unwanted reaction products. A series of batch and column experiments were performed with varying H2O2 concentrations to decompose selected chlorinated ethylenes. Either dissolved iron from soil or iron sulfate salt was added to provide the iron catalyst in the batch tests. Batch experiments revealed that both citric and sulfuric acid systems achieved over 90% contaminant removal rates, and the presence of iron catalyst was essential for effective decontamination. Batch tests with citric acid showed no signs of pressure accumulation and solid precipitations, however the results suggested that an excessive usage of H2O2 relative to iron catalysts (Fe2+/H2O2<1/330) would result in lowering the efficiency of contaminant removal by iron chelation in the citric acid system. Column tests confirmed that citric acid could provide suitable acidic conditions to achieve higher than 55% contaminant removal rates.     

Effects of operating parameters on advanced oxidation of diuron by the Fenton's reagent: a statistical design approach

Advanced oxidation of diuron in aqueous solution by Fenton's reagent using FeSO(4) as source of Fe(II) was investigated in the absence of light. Effects of operating parameters namely the concentrations of pesticide (diuron), H(2)O(2) and Fe(II) on oxidation of diuron was investigated by using Box-Behnken statistical experiment design and the surface response analysis. Diuron oxidation by the Fenton reagent was evaluated by determining the total organic carbon (TOC), diuron, and adsorbable organic halogen (AOX) removals. Concentration ranges of the reagents resulting in the highest level of diuron oxidation were determined. Diuron removal increased with increasing H(2)O(2) and Fe(II) concentrations up to a certain level. Diuron concentration had a more profound effect than H(2)O(2) and Fe(II) in removal of diuron, TOC and AOX from the aqueous solution. Nearly complete (98.5%) disappearance of diuron was achieved after 15min reaction period. However, only 58% of diuron was mineralized after 240min under optimal operating conditions indicating formation of some intermediate products. Optimal H(2)O(2)/Fe(II)/diuron ratio resulting in the maximum diuron removal (98.5%) was found to be 302/38/20 (mgl(-1)).     

Kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE)

The kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE) in aqueous solutions at various pH, temperature, oxidant concentration and ionic strength levels was studied. The MTBE degradation was found to follow a pseudo-first-order decay model. The pseudo-first-order rate constants of MTBE degradation by persulfate (31.5 mM) at pH 7.0 and ionic strength 0.11 M are approximately 0.13 x 10(-4), 0.48 x 10(-4), 2.4 x 10(-4) and 5.8 x 10(-4) S(-1) at 20, 30, 40 and 50 degrees C, respectively. Under the above reaction conditions, the reaction has an activation energy of 24.5 +/- 1.6 kcal/ mol and is influenced by temperature, oxidant concentration, pH and ionic strength. Raising the reaction temperature and persulfate concentration may significantly accelerate the MTBE degradation. However, increasing both pH (over the range of 2.5-11) and ionic strength (over the range of 0.11-0.53 M) will decrease the reaction rate. Reaction intermediates including tert-butyl formate, tert-butyl alcohol, acetone and methyl acetate were observed. These intermediate compounds were also degraded by persulfate under the experimental conditions. Additionally, MTBE degradation by persulfate in a groundwater was much slower than in phosphate-buffer solutions, most likely due to the presence of bicarbonate ions (radical scavengers) in the groundwater.     

UV/Fenton氧化降解水溶液中甲基叔丁基醚的试验研究

采用UV／Fenton技术对污染水体中的甲基叔丁基醚（MTBE）进行了氧化降解试验。结果表明，在室温条件下，当H2O2为10mmol／L，FC＋为2mmol／L，pH为2．4时，起始摩尔浓度为1mmol／L的MTBE在30min内可去除99％；结果还显示了MTBE的降解分两个阶段，第一阶段是在UV／Fe^2＋／H2O2下的快速降解，第二阶段由于Fe^2＋的大量消耗而降解相对较慢。     

Mechanism for the destruction of carbon tetrachloride and chloroform DNAPLs by modified Fenton's reagent

The destruction of a carbon tetrachloride DNAPL and a chloroform DNAPL was investigated in reactions containing 0.5 mL of DNAPL and a solution of modified Fenton's reagent (2M H2O2 and 5mM iron(III)-chelate). Carbon tetrachloride and chloroform masses were followed in the DNAPLs, the aqueous phases, and the off gasses. In addition, the rate of DNAPL destruction was compared to the rate of gas-purge dissolution. Carbon tetrachloride DNAPLs were rapidly destroyed by modified Fenton's reagent at 6.5 times the rate of gas purge dissolution, with 74% of the DNAPL destroyed within 24h. Use of reactions in which a single reactive oxygen species (hydroxyl radical, hydroperoxide anion, or superoxide radical anion) was generated showed that superoxide is the reactive species in modified Fenton's reagent responsible for carbon tetrachloride DNAPL destruction. Chloroform DNAPLs were also destroyed by modified Fenton's reagent, but at a rate slower than the rate of gas purge dissolution. Reactions generating a single reactive oxygen species demonstrated that chloroform destruction was the result of both superoxide and hydroxyl radical activity. Such a mechanism of chloroform DNAPL destruction is in agreement with the slow but relatively equal reactivity of chloroform with both superoxide and hydroxyl radical. The results of this research demonstrate that modified Fenton's reagent can rapidly and effectively destroy DNAPLs of contaminants characterized by minimal reactivity with hydroxyl radical, and should receive more consideration as a DNAPL cleanup technology.     

Low-pressure catalytic wet-air oxidation of a high-strength industrial wastewater using Fenton's reagent.

Wastewater from the Afyon Alkaloids Factory (Afyon, Turkey) was subjected to low-pressure catalytic wet-air oxidation (CWAO) using Fenton's reagent, and the optimal reaction conditions were investigated. The CWAO using Fenton's reagent was applied to the factory effluent, diluted factory effluent, and aerobically pretreated wastewater. To find the optimum quantities of reagents, ferrous iron (Fe(+2))-to-substrate ratios of 1:10, 1:25, and 1:50 and hydrogen peroxide (H2O2)-to-Fe(+2) ratios of 1, 5, and 10 were investigated, and the treatment was carried out at different temperatures. High chemical oxygen demand (COD) removals were obtained at 50 degrees C, with the Fe(+2)-to-substrate ratio range between 1:10 and 1:25. The change in H2O2-to-Fe(+2) ratios did not cause any considerable effect. Also, the percentages of COD removals were nearly the same, so the ratio H2O2:Fe(+2):1 is recommended. Aerobic pretreatment seems to be effective. On the other hand, no enhancement was observed in the case of the diluted wastewater.     

Degradation of the herbicide 2,4-DP by anodic oxidation, electro-Fenton and photoelectro-Fenton using platinum and boron-doped diamond anodes

This paper reports the degradation of 2,4-DP (2-(2,4-dichlorophenoxy)-propionic acid) solutions of pH 3.0 by environmentally friendly electrochemical methods such as anodic oxidation, electro-Fenton and photoelectro-Fenton with a Pt or boron-doped diamond (BDD) anode. In the two latter techniques an O(2)-diffusion cathode was used and 1.0mM Fe(2+) was added to the solution to give hydroxyl radical (*OH) from Fenton's reaction between Fe(2+) and H(2)O(2) generated at the cathode. All treatments with BDD are viable to decontaminate acidic wastewaters containing 2,4-DP since they give complete mineralization, with loss of chloride ion, at high current due to the great production of oxidant *OH at the BDD surface favoring the destruction of final carboxylic acids. *OH formed from Fenton's reaction destroys more rapidly aromatic products, making the electro-Fenton and photoelectro-Fenton processes much more efficient than anodic oxidation. UVA light in photoelectro-Fenton with BDD has little effect on the degradation rate of pollutants. The comparative procedures with Pt lead to slower decontamination because of the lower oxidizing power of this anode. The effect of current on the degradation rate and efficiency of all methods is studied. The 2,4-DP decay always follows a pseudo-first-order kinetics. Chlorohydroquinone, chloro-p-benzoquinone and maleic, fumaric, malic, lactic, pyruvic, acetic, formic and oxalic acids are detected as products by chromatographic techniques. A general sequence accounting for by the reaction of all these intermediates with the different oxidizing agents is proposed.     

An unconventional approach to studying the reaction kinetics of the Fenton's oxidation of 2,4-dichlorophenoxyacetic acid

The Fenton's oxidation kinetics of herbicide 2,4-D at various [Fe(II)] and [H(2)O(2)] combinations was investigated and modelled through an unconventional approach. The reaction kinetics of 2,4-D degradation demonstrated a two-stage pattern of decay, where a very fast reactive stage was followed by a retardation stage due to the depletion of oxidants and to the competitive side-reactions of the intermediates (including 2,4-dichlorophenol, chlorohydroquinone and 2,6-dichlororesorcinol). A model characterized by two newly established constants, the initial decay rate and the maximum oxidative capacity, was proposed and proven capable of describing the two-stage process, which cannot easily be described by conventional first- or second-order kinetics approaches.     

Enhanced chemical oxidation of aromatic hydrocarbons in soil systems

Fenton's destruction of benzene, toluene, ethylbenzene, and xylene (BTEX) was investigated in soil slurry batch reactors. The purpose of the investigation was to quantify the enhancement of oxidation rates and efficiency by varying process conditions such as iron catalyst (Fe(II) or Fe(III); 2, 5, and 10mM), hydrogen peroxide (H2O2; 30, 150, 300 mM), and metal chelating agents (l-ascorbic acid, gallic acid, or N-(2-hydroxyethyl)iminodiacetic acid). Rapid contaminant mass destruction (97% after 3h) occurred in the presence of 300 mM H2O2 and 10 mM Fe(III). An enhanced removal rate (>90% removal after 15 min and 95% removal after 3h) was also observed by combining Fe(III), N-(2-hydroxyethyl)iminodiacetic acid and 300 mM H2O2. The observed BTEX mass removal rate constants (3.6-7.8 x 10(-4)s(-1)) were compared to the estimated rate constants (4.1-10.1 x 10(-3)s(-1)). The influence of non-specific oxidants loss (by reaction with iron hydroxides and soil organic matter) was also explored.     

Mineralization of dinitrotoluenes and trinitrotoluene of spent acid in toluene nitration process by Fenton oxidation

Fenton's reagent, UV/H2O2 and UV/Fenton's reagent were employed to mineralize dinitrotoluene (DNT) isomers and 2,4,6-trinitrotoluene (TNT) of spent acid in toluene nitration process. The bench-scale experiments were conducted to elucidate the influence of various operating variables on the performance of removal of total organic compounds (TOC) from spent acid, including reaction temperature, concentration of ferrous ion and H2O2 dosage. It is remarkable that organic compounds were completely mineralized by Fenton oxidation, of which removal efficiency is superior to that of UV/H2O2. Nevertheless, it makes slight difference between Fenton oxidation and UV/Fenton oxidation. According to the spectra identified by gas chromatograph/mass spectrometer (GC/MS), it is proposed that oxidative degradation of DNT isomers leads to o-, m-, p-mononitrotoluene (MNT) and 1,3-dinitrobenzene respectively. Besides, the oxidation of 2,4,6-TNT gives the 1,3,5-trinitrobenzene intermediate. Apparently, Fenton oxidation is promising for purification of spent acid industrially.     

A comparative study of the effects of chloride, sulfate and nitrate ions on the rates of decomposition of H2O2 and organic compounds by Fe(II)/H2O2 and Fe(III)/H2O2

The effects of chloride, nitrate, perchlorate and sulfate ions on the rates of the decomposition of hydrogen peroxide and the oxidation of organic compounds by the Fenton's process have been investigated. Experiments were conducted in a batch reactor, in the dark at pH < or = 3.0 and at 25 degrees C. Data obtained from Fe(II)/H2O2 experiments with [Fe(II)]0/[H2O2]0 > or = 2 mol mol(-1), showed that the rates of reaction between Fe(II) and H2O2 followed the order SO4(2-) > ClO4(-) = NO3- = Cl-. For the Fe(III)/H2O2 process, identical rates were obtained in the presence of nitrate and perchlorate, whereas the presence of sulfate or chloride markedly decreased the rates of decomposition of H2O2 by Fe(III) and the rates of oxidation of atrazine ([atrazine]0 = 0.83 microM), 4-nitrophenol ([4-NP]0 = 1 mM) and acetic acid ([acetic acid]0 = 2 mM). These inhibitory effects have been attributed to a decrease of the rate of generation of hydroxyl radicals resulting from the formation of Fe(III) complexes and the formation of less reactive (SO4(*-)) or much less reactive (Cl2(*-)) inorganic radicals.     

Decolorization and degradation of H-acid and other dyes using ferrous-hydrogen peroxide system

In this study, advanced oxidation process utilizing Fenton's reaction was investigated for the decolorization and degradation of two commercial dyes viz., Red M5B, Blue MR and H-acid, a dye intermediate used in chemical industries for the synthesis of direct, reactive and azo dyes. Effect of Fe2 +, H2O2, pH, and contact time on the degradation of the dyes was studied. Maximum color and COD removal was obtained for Red MSB, H-acid and Blue MR at 10-25 mg/l of Fe2+ dose and 400-500 mg/l of H2O2 dose at pH 3.0. The initial oxidation reaction was found to fit into first order rate kinetics and the rate of oxidation of H-acid was higher than the other dyes. Release of chloride and sulfate from the Fenton's treated Red M5B dye and sulfate from H-acid and Blue MR indicates that the dye degradation proceeds through cleavage of the substituent group.     

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*).     

Simultaneous decontamination of hexavalent chromium and methyl tert-butyl ether by UV/TiO2 process

Hexavalent chromium and methyl tert-butyl ether (MTBE) are two important environmental pollutants. Simultaneous decontamination of Cr(VI) and MTBE was studied by UV/TiO2 process. The influences of pH and the concentrations of pollutants on the kinetics of the photocatalytic reactions were evaluated. Dark adsorption tests showed that the acidic pH favored the adsorption of Cr(VI) while neutral pH favored the adsorption of MTBE. Under UV irradiation, Cr(VI) reduction was observed in Cr(VI)/TiO2 system, and MTBE oxidation was observed in MTBE/TiO2 system. The system containing Cr(VI) and MTBE by UV/TiO2 process demonstrated the synergistic effect between oxidation of MTBE and reduction of Cr(VI). The results demonstrated that two pollutants Cr(VI) and MTBE could be eliminated simultaneously by UV/TiO2 process. tert-Butyl formate, tert-butyl alcohol and acetone were identified as primary degradation products of MTBE by gas chromatography-mass spectrometry in the degradation of MTBE by UV/TiO2 process.     

Electrocatalytic oxidation of methyl tert-butyl ether (MTBE) in aqueous solution at a nickel electrode

This study utilized the electrocatalytic characteristics of nickel electrode to perform degradation of methyl tert-butyl ether (MTBE) in aqueous solution. Lab experiments were conducted in a spiltless bath type cell equipped with a nickel electrode as working electrode, a platinum wire as counter electrode, and an Ag/AgCl electrode as reference electrode. Effects of controlled potential, supporting electrolyte, and solution pH on the efficiency of MTBE removal were examined under the control of the constant-potential conditions. Experiment results showed that the optimum electrolytic condition was operated at 0.35 V in a 1M KOH electrolyte solution, and the initial 20 mgl(-1) MTBE was reduced by 73% within 180 min under the optimum control. As using 1M Na2SO4 and 1M KCl as electrolyte, the efficiency of MTBE removal dropped to 60% and 50% under the similar controls. Comparing with various pH controls, the strong basic condition is favorable for electrocatalytic oxidation of MTBE in the Ni-electrolytic system. The efficiency of MTBE removal showed a rising trend with increasing initial pH of the solution. The formation of a redox NiOOH/Ni(OH)2 layer on the anode surface, which was observed on the SEM image, can explain that nickel plays a mediator role on improving electrocatalytic oxidation of MTBE at 0.35 V in a strong basic condition. The by-products of MTBE degradation were identified as acetone and CO(2) by GC/MS, and the distributions of carbon atoms in acetone, CO2, and MTBE were found 22%, 51%, and 27% through the optimum control of electrochemical oxidation.     

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.     

Enhanced Fenton's destruction of non-aqueous phase perchloroethylene in soil systems

The Fenton's system is applied to the destruction of perchloroethylene (PCE) present as a dense non-aqueous phase liquid (DNAPL) in soil slurry systems; the initial concentration of PCE was 45 times higher than its aqueous solubility. Studies were conducted in two matrices: Ottawa sand and soil from Warsaw, IN. In Ottawa sand, a 60-62% decrease in PCE concentration was observed, and Cl(-) recovery was 47-58%, whereas in Warsaw soil, a 44-49% decrease in PCE concentration and a Cl(-) recovery of 40-42% were observed after the addition of 600 mM H(2)O(2) and 10 mM dissolved iron. Significantly enhanced destruction resulted during application of N-(2-hydroxyethyl) iminodiacetic acid (HEIDA) to Warsaw soil. For example, in the absence of HEIDA in Warsaw soil, 36% PCE loss and 33% Cl(-) release were observed at 600 mM H(2)O(2) and 5 mM Fe(III), while 74% PCE loss and 63% Cl(-) release were achieved at 600 mM H(2)O(2) and 5 mM Fe(III)-HEIDA. For both soils, the catalytic activities of Fe(II) and Fe(III) were nearly equivalent. These findings clearly demonstrate that system design can be optimized with regard to process variables in Fenton's treatment of DNAPL in soils.     

Effect of chlorides and sulfates on the performance of a Fe3+/H2O2 Fenton-like system in the degradation of methyl tert-butyl ether and its byproducts.

The effect of chloride and sulfate ions on the oxidation of methyl tert-butyl ether (MTBE) and its degradation products in a Fenton-like system was studied. Although both chloride and sulfate ions inhibited the decomposition of H202, chlorides were found to be the more effective inhibitor of MTBE degradation. In the presence of sulfates, MTBE decomposition can be attributed to oxidation not only by hydroxyl radicals, but also likely by SO4*- species. In the presence of chloride ions, it is possible that the dichloride radical is formed, which is less reactive than OH*. In the system under investigation, t-butyl alcohol was found to be the major byproduct, followed by t-butyl formate and acetone. The degradation rates of all intermediates and their inhibition in the presence of inorganic ions are similar to those obtained for MTBE, although their distributions are related to the concentrations of inorganic salts added.     

Fenton's pre-treatment of mature landfill leachate

The aim of this study was to check the effectiveness of the Fenton's reagent (Fe2+ + H2O2 + H+) for the pre-treatment of a municipal landfill leachate with the objective of improving its overall biodegradability, evaluated in terms of BOD5/COD ratio, up to a value compatible with biological treatment. The leachate came from a municipal sanitary landfill located in southern Italy and the average values of its main parameters were: pH=8.2; COD=10,540 mgl(-1); BOD5=2,300 mgl(-1); TOC=3,900 mgl(-1); NH4-N=5210 mgl(-1); conductivity=45,350 microScm(-1); alkalinity=21,470 mgl(-1) CaCO3. The effect of initial pH value on the pre-treatment effectiveness was evaluated by titrating the amount of acidic by-products formed. The extent of leachate oxidation was monitored and controlled by both pH and redox potential measurements. The best operational conditions for achieving the desired goal (i.e., BOD5/COD> or =0.5) resulted: Fe2+=275 mgl(-1); H2O2=3,300 mgl(-1); initial pH=3; reaction time=2 h. At the end of the Fenton's pre-treatment, in order to permit a subsequent biological treatment, residual ferric ions were removed increasing the pH up to 8.5 by adding 3 gl(-1) of Ca(OH)2 and 3 mgl(-1) of a cationic polyelectrolyte, the latter as an aid to coagulation. This final step also resulted in a further modest removal of residual COD due to co-precipitation phenomena.