Anodic Fenton Treatment Research Articles

High removal efficiency of dye pollutants by anodic Fenton treatment

High removal efficiency of dye pollutants by anodic Fenton treatment

Electrochemical Reduction of Acetochlor at Carbon and Silver Cathodes in Dimethylformamide

Chloroacetamides are a popular class of herbicides often used against weeds in a variety of major crops, such as corn, cotton, rice, and soybeans.1 One such herbicide is acetochlor or 2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)acetamide that, since its registration in 1994, has become commonly used in the United States.2 Although acute and chronic toxicological effects in humans of acetochlor at low environmental exposures are still unknown, animal tests have shown in some species the development of lung tumors, nasal epithelia, and thyroid cancer; for that reason, the U.S. EPA classifies acetochlor as likely to be carcinogenic in humans.3,4 This project’s primary objective is to investigate the electrochemical behavior of acetochlor and to develop a possible degradation method for acetochlor as well as other chloroacetamide-type herbicides. To the best of our knowledge, previous electrochemical studies of acetochlor have been performed only via anodic Fenton treatment;5 electrochemical reduction has not yet been pursued. In the present study, we have conducted cyclic voltammetry to evaluate the electrochemical behavior of acetochlor at carbon and silver cathodes in dimethylformamide (DMF) containing 0.05 M tetramethylammonium tetrafluoroborate (TMABF4). Glassy carbon is a traditional electrode material and silver has been shown to be catalytic for the cleavage of carbon–halogen bonds. Reduction of acetochlor at silver (–0.95 V vs. Cd/Hg) occurs at more positive potentials than at carbon (–1.4 V vs. Cd/Hg) and affords primarily the dechlorinated parent compound, N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)acetamide. In addition, reduction of acetochlor in the presence of electrogenerated nickel(I) salen (–0.95 V vs. Cd/Hg) indicates that nickel salen complexes can be an alternative to silver in order to achieve catalytic reduction. Controlled-potential (bulk) electrolysis coupled with traditional analytical methods such as gas chromatography–mass spectrometry (GC–MS) led to the identification and quantitation of reduction products. References Lamberth, C. Chloroacetamide Herbicides. In Bioactive Carboxylic Compound Classes, Pharmaceuticals and Agrochemicals, Lamberth, C., Dinges, J., Eds.; Wiley: Germany, 2016; pp 293–302.Lerro, C. C.; Koutros, S.; Andreotti, G.; Hines, C. J.; Blair, A; Lubin, J.; Ma, X.; Zhang, Y.; Beane Freeman, L. E. Int. J. Cancer. 2015, 137, 1167–1175.U.S. Environmental Protection Agency. Acetochlor (Harness) Pesticide Petition Filing 1/00. Fed Regist. 2000, 65, 3682–3690. Report of the Food Quality Protection Act (FQPA) Tolerance Reassessment Progress and Risk Management Decision (TRED) for Acetochlor. EPA 738-R-00-009; U.S. Environmental Protection Agency (U.S. EPA): 2006, 1–9.Friedman, C. L.; Lemley, A. T.; Hay, A. J. Agric. Food Chem. 2006, 54, 2640–2651.

AuPd/Fe3O4-based three-dimensional electrochemical system for efficiently catalytic degradation of 1-butyl-3-methylimidazolium hexafluorophosphate

Ionic liquids (ILs) have been reported to be toxic and harmful to aquatic and terrestrial organisms, thus it is imperative to remove the residual ILs in various effluents. In this work, a three-dimensional (3D) electrocatalytic system with synthesized AuPd/Fe3O4 nanoparticles (NPs) as particle electrodes (PEs) was established for the degradation of typical 1-butyl-3-methylimidazolium ([BMIM]) based ILs. The as-synthesized AuPd/Fe3O4 possessed preferable electrochemical properties for in situ supplement of H2O2 and renewable Fe species. This 3D electrocatalytic system exhibited excellent performance with 100% removal rate of BMIM in 90min under 120mA, pH 3, and 1g/L dosage of AuPd/Fe3O4 NPs. Kinetics study revealed that the degradation rule of BMIM well followed the anodic Fenton treatment (AFT) model, in which the variation of the degradation rate was positively correlated with that of dissolved Fe2+, while significantly differed from the evolution of H2O2. Particularly, the appearance of the H2O2 inflection point suggested the optimal effectiveness of AuPd/Fe3O4-based 3D electrocatalysis. During this electrocatalytic process, the active HO was produced over the AuPd/Fe3O4 PEs, thereby initiated the highly efficient degradation of BMIM into 1-butyl-3-methyl-2,4,5-trioxoimidazolidine, 1-butyl-3-methylurea and N-butyl-formamide as main intermediates. The electrocatalytic stability of the AuPd/Fe3O4 PEs over seven times further indicated the potential applicability for organic wastewater treatment.

Species-Dependent Degradation of Ciprofloxacin in a Membrane Anodic Fenton System

The anodic Fenton treatment method (AFT) has been successfully applied to the removal of ciprofloxacin (CIP), a widely used fluoroquinolone antibiotic, from aqueous solution. Degradation kinetics were found to be species dependent. At initial pH 3.2, CIP remained in its cationic form and the kinetics followed a previously developed AFT model. At an initial near-neutral pH, CIP speciation changed during the degradation, due to pH changes over the process, and no obvious model fit the data. Density functional theory (DFT) calculations indicated a protonated species-dependent reaction affinity toward hydroxyl radicals. A new model based on the AFT model with the addition of species distribution during the degradation was derived, and it was shown to describe the degradation kinetics successfully. Degradation of reference compounds further confirmed that the free carboxylic acid group, which contributes to the species changes, plays a key role in the observed degradation pattern. Furthermore, degradation of reference CIP-metal complexes confirmed that the formation of these complexes does not have a major effect on the degradation pattern. Optimization of CIP degradation was carried out at pH 3.2 with an optimal H2O2/Fe2+ ratio found between 10:1 and 15:1. Three degradation pathways based on mass spectrometry data were also proposed: (1) hydroxylation and defluorination on the aromatic ring; (2) oxidative decarboxylation; and (3) oxidation on the piperazine ring and dealkylation. By the end of the AFT treatment, neither CIP nor its degradation products were detected, indicating successful removal of antibacterial properties.

Degradation of Sulfonamides in Aqueous Solution by Membrane Anodic Fenton Treatment

Two agricultural antibiotics used heavily in agriculture, sulfamethazine and sulfadiazine, were degraded in an aqueous system by anodic Fenton treatment (AFT), an advanced oxidation technique that has been shown to be effective in degrading various pesticides but has not been applied to antibiotics. The effects of the H(2)O(2)/Fe(2+) ratio, Fe(2+) delivery rate, and initial contaminant concentration on the degradation of sulfamethazine by AFT were determined. The optimal H(2)O(2)/Fe(2+) ratio was determined to be 10:1, and the optimal Fe(2+) delivery rate was found to be between 38.9 and 54.4 microM min(-1). Under these conditions, sulfamethazine was completely degraded within 10 min at a range of concentrations (18-250 microM) commonly found in manure lagoons, contaminated rivers, and groundwater. Using the same optimal conditions, the effect of pH on the degradation of sulfadiazine by AFT was analyzed, and 100 microM sulfadiazine was degraded within 6-8 min of treatment at a range of pH values (3.1-7.1) that could potentially be found in aquatic environments. Degradation products and pathways were proposed for both compounds, and it was inferred that AFT degradation products of sulfadiazine and sulfamethazine are unlikely to retain the bacteriostatic properties of their parent compounds. An aquatic toxicity test employing Lemna gibba confirmed that AFT removes the bacteriostatic properties of sulfamethazine and sulfadiazine during degradation.

Adsorption effect on the degradation of 4,6- o-dinitrocresol and p-nitrophenol in a montmorillonite clay slurry by AFT

The adsorption and degradation of 4,6- o-dinitrocresol (DNOC) and p-nitrophenol (PNP) in SWy-2 montmorillonite clay slurry were investigated. The pH and type of cation of the slurry were varied. Results showed that adsorption of DNOC and PNP increased at lower pH values, and when pH < p K a (4.4) of DNOC, DNOC was almost completely adsorbed on the clay under given experimental conditions. The specific cation also had a significant effect on adsorption, which was dramatically enhanced in the presence of K + and NH 4 +, compared with the presence of Na + or Ca 2+. Anodic Fenton treatment (AFT) degradation of DNOC and PNP in the clay slurry was studied, and it was found that DNOC degradation rates were greatly affected by the initial pH and the types of electrolytes. Due to the higher adsorption, the degradation rate substantially decreased in the clay slurry system in the presence of K + and low pH, with a large amount of DNOC residue remaining after 60 min treatment. AFT degradation of PNP was completed within 30 min treatment. Based on LC–MS data, a DNOC degradation pathway was proposed. Overall, the results showed the inhibition effect of adsorption on the degradation of nitroaromatic compounds in montmorillonite clay slurry by AFT, providing important implications for water and soil remediation.

Kinetics of Carbaryl Degradation by Anodic Fenton Treatment in a Humic‐Acid‐Amended Artificial Soil Slurry

A Fenton-based indirect electrochemical method, anodic Fenton treatment (AFT), developed for destroying and detoxifying pesticides in the aqueous environment, was evaluated for the degradation of a widely used pesticide, carbaryl, in an artificial soil slurry. More than 90% of carbaryl was removed in less than 20 minutes under given experimental conditions. The effect of initial slurry pH, humic acid content, initial carbaryl concentration, Fenton reagent delivery ratio, and soil/water ratio (w/v) were investigated. The results indicate that humic acid content is the key factor that slows down pesticide degradation, most probably because of its pH buffering and adsorption capacity. A kinetic model, which was shown to fit the experimental data quite well (R2 > 0.99), was developed to describe the carbaryl degradation in the soil slurry during the AFT process. In the presence of humic acid, carbaryl degradation kinetics was found to shift to a pseudo-first-order reaction after an "initiation" stage.

Adsorption Effect on the Degradation of Carbaryl, Mecoprop, and Paraquat by Anodic Fenton Treatment in an SWy-2 Montmorillonite Clay Slurry

The Fenton reaction-based anodic Fenton treatment (AFT) was applied to three widely used organic agrochemicals, carbaryl, mecoprop, and paraquat, in a clay slurry. The adsorption and degradation behaviors of these neutral (carbaryl), anionic (mecoprop), and cationic (paraquat) agrochemicals were studied in a slurry of SWy-2 Na(+)-montmorillonite clay, and adsorption isotherms were obtained at given experimental conditions. The d spacing (d 001) of the clay layer before and after adsorption or degradation was measured by X-ray diffraction (XRD). On the basis of the change of d spacing, molecular disposition at the clay interlayer was inferred: both mecoprop and paraquat form a monolayer sitting flat and parallel to the clay siloxane surfaces. Results show that, due to different adsorption mechanisms, the adsorption effect on chemical degradation by AFT varies with pesticide: strong and tight adsorption of paraquat at the clay interlayer protects paraquat from being attacked by hydroxyl radicals; loosely adsorbed carbaryl or mecoprop is readily degraded. XRD analysis clearly indicates that AFT is capable of effectively degrading interlayer noncationic organic chemicals that are not usually available for biodegradation.

Effect of nonionic surfactants on the oxidation of carbaryl by anodic Fenton treatment

As a potentially promising technology, anodic Fenton treatment (AFT) has been shown to be very successful in pesticide removal. However, the influence of other constituents in the pesticide formulation, such as nonionic surfactants, has not been addressed. In this study, the effect of Triton X (TX) on the degradation kinetics and pathways of carbaryl undergoing AFT was investigated in an effort to facilitate its practical application. The presence of Triton X-100 was found to slow down the carbaryl degradation rate. This result can be attributed to the consumption of hydroxyl radicals ( OH) by surfactants and the formation of a carbaryl⋯TX⋯Fe 3+ complex, resulting in the unavailability of carbaryl to OH attack. The modified AFT kinetic model previously developed in this laboratory shows an excellent fit to the carbaryl degradation profile ( R 2>0.998), supporting the formation of a carbaryl⋯TX⋯Fe 3+ complex. The carbaryl degradation rate decreased as Triton X-100 concentration increased from 20 to 1000 mg L −1. Both OH consumption by surfactants and complex formation are responsible for the degradation rate reduction below the critical micelle concentration (CMC), whereas the complex and micelle formation becomes a more dominant factor above the CMC. The effect of ethylene oxide (EO) numbers of a given nonionic surfactant mainly lies in the consumption of hydroxyl radicals, which increases with the length of the EO chain, but does not significantly affect the formation of the carbaryl⋯TX⋯Fe 3+ complex. Based on the GC–MS and LC–ESI–MS results, no evidence was found that the carbaryl degradation pathway was affected. Carbaryl was typically oxidized to 1-naphthol and 1,4-naphthoquinone similar to what is observed in the absence of surfactants. Triton X-100 was degraded via the breakdown of EO chains and ω-oxidation of the terminal methyl group, which resulted in the production of a series of ethoxylate oligomers.

Evaluation of the Performance of Flow-through Anodic Fenton Treatment in Amide Compound Degradation

A flow-through anodic Fenton treatment (FAFT) system based on the batch AFT technology was previously developed to degrade pesticides in aqueous solution. As one of a series of benchtop and pilot-scale studies in process optimization, the goal of the reported work is to evaluate the performance of the FAFT system under various operating conditions, which is critical to bringing this technology into practical general use in the field. For this purpose, the removal efficiency of the parent pesticide and the concentration of the hydroxyl radical in FAFT were calculated on the basis of a previously developed FAFT kinetic model and used for the evaluation. N,N-Diethyl-3-methylbenzamide (DEET), an insect repellent, was used as a chemical probe. Experimental data showed that the key to a high treatment efficiency is to operate the FAFT system to achieve a maximum *OH production with a minimum input of energy and chemicals. For the anodic half-cell, the system should be operated under flow-through conditions with a self-developed optimum pH of 3.0, a relatively high flow rate, and the initial effluent recycled within 6-10 min to the FAFT system for further treatment; for the cathodic half-cell, it should have a fixed volume and be entirely replaced by another batch of cathodic solution only when the pH reaches a very high value. The delivery rate of the ferrous iron should be maintained at an electrolytic current between 0.01 and 0.02 A; the ratio of H2O2/Fe2+ should be between 5:1 and 10:1. NaCl was found to be the best electrolyte, with concentrations of 0.01-0.02 and 0.08 M in the anodic and cathodic half-cells, respectively. The FAFT system was successfully applied to degrade various model amide compounds and DEET formulations, which suggests the likelihood of extending this approach to other pesticide-containing wastewaters.

Degradation of methyl tertiary-butyl ether (MTBE) by anodic Fenton treatment

Degradation of MTBE, a common fuel oxygenate, was investigated using anodic Fenton treatment (AFT) and by comparison with classic Fenton treatment (CFT). The AFT system provided an ideal pH environment (2.5–3.5) for the Fenton reaction and utilized gradual delivery of ferrous iron and hydrogen peroxide, which was more efficient than batch CFT to degrade MTBE and its breakdown products. The optimized ratio of ferrous iron to hydrogen peroxide for AFT was determined to be 1:5 (in mmol). Depending on the initial concentration, MTBE was completely degraded by the optimized AFT in 4–8 min. The breakdown products found during the treatment of MTBE were acetone, t-butyl formate, t-butanol, methyl acetate, acetic acid, and formic acid, which were all completely degraded by the optimized AFT in 32 min. Based on the experimental results and other work reported in the literature, degradation mechanisms of MTBE and its breakdown products in AFT and CFT were proposed. Generally, reactions are initiated by H-abstraction by OH, generating carbon-centered radicals which undergo various reactions including α/β-scission within the radical, combination with oxygen, oxidation by ferric ion, and reduction by ferrous ion before generating the final oxidation products. Radical combination with oxygen (and the reactions thereafter) and radical oxidation by ferric ion are believed to be the most important pathways in the overall fate of the generated radicals, while radical reduction by ferrous ion is the least important. By elucidating the reaction kinetics and mechanisms of MTBE degradation in the anodic Fenton system, this study offers a potential remediation technique for treating MTBE-contaminated wastewater.

Modeling Evaluation of Carbaryl Degradation in a Continuously Stirred Tank Reactor by Anodic Fenton Treatment

Anodic Fenton treatment (AFT) has been shown to be effective in removing pesticides from aqueous solution in batch reactors with the formation of less toxic and more biodegradable products. To facilitate practical application of AFT, carbaryl degradation in a continuously stirred tank reactor (CSTR) by AFT was investigated under different experimental conditions, such as carbaryl inlet concentration, Fenton reagent concentration/ratio, and carbaryl feeding flow rate. A higher Fe2+ delivery rate and H2O2 to Fe2+ ratio (H2O2:Fe2+) were found to favor the carbaryl degradation process, whereas flow rate was shown to be a much less significant factor to influence the degradation rate under the evaluated experimental conditions. A kinetic-based semiempirical model was developed to simulate the experimental data, and a very good fit between the model and the raw data was found (R2 > 0.99). A dimensionless parameter (k/q2) was found to be a good indicator of the degradation rate; that is, the higher the k/q2value is, the faster the degradation process is. The rate parameter (k) can be used to evaluate the degradation rate when the flow rate is invariant for a given pesticide. The shape parameter (beta) is most likely related to the availability and reactivity of Fenton reagents and hydroxyl radicals. To compare the degradation rate of different pesticides, more information other than k/q2, k, and beta values, such as the instantaneous degradation rate vs time relationship, needs to be considered.

Reaction Mechanism and Kinetic Modeling of DEET Degradation by Flow-Through Anodic Fenton Treatment (FAFT)

The previously developed batch anodic Fenton treatment (AFT) technology has been successfully applied to degrade various pesticides in aqueous solution. The goal of this work is the development of a flow-through AFT system (FAFT) which is critical to bringing this technology into practical general use in the field. For this purpose, the degradation of DEET (N,N-diethyl-3-methylbenzamide), an insect repellent, and nine model amides was studied. Oxidation products of these compounds in FAFT were identified by GC/MS, and the results revealed that various -OH additions (most likely on the aromatic ring), quinone/keto product formation, and dimerization/bimolecular disproportionation are the major reaction pathways. This proposed overall reaction mechanism was then combined with the basic Fenton's mechanism to model the kinetics of various active species in FAFT including DEET, Fe2+, H2O2, and total iron under different reaction conditions. In addition, both initial and steady-state hydroxyl radical concentrations were measured in FAFT using benzoic acid as a chemical probe; the measured *OH concentrations were best-fitted exponentially. On the basis of the obtained [*OH] trend and the mass balance of the FAFT system, a simple FAFT model was developed to fit all of the degradation data of DEET and the model amides.

Kinetic Modeling of 2,4-Dichlorophenoxyacetic Acid (2,4-D) Degradation in Soil Slurry by Anodic Fenton Treatment

Anodic Fenton treatment (AFT) has been shown to be a promising technology in pesticide wastewater treatment. However, no research has been conducted on the AFT application to contaminated soils. In this study, the 2,4-D degradation kinetics of AFT in a silt loam soil slurry were investigated for the first time, and the effects of various experimental conditions including initial 2,4-D concentration, Fenton reagent delivery rate, amount of humic acid (HA) addition, and pH were examined. The 2,4-D degradation in soil slurry by AFT was found to follow a two-stage kinetic model. During the early stage of AFT (the first 4-5 min), the 2,4-D concentration profile followed a pseudo-first-order kinetic model. In the later stage (typically after 5 or 6 min), the AFT kinetic model provided a better fit. This result is most likely due to the existence of (*)OH scavengers and 2,4-D sorption on soil. The Fe(2+) delivery rate was shown to be a more significant factor in degradation rate than the H(2)O(2) delivery rate when the Fe(2+)/H(2)O(2) ratios were in the range of 1:2 to 1:10. The presence of HA in soil lowered the AFT rate, most probably due to the competition with 2,4-D for consumption of (*)OH and increased sorption of 2,4-D on soil. The optimal pH for 2,4-D degradation in soil slurry by AFT was observed to be in the range of pH 2-3.

Degradation of Chloroacetanilide Herbicides by Anodic Fenton Treatment

Anodic Fenton treatment (AFT) is an electrochemical treatment employing the Fenton reaction for the generation of hydroxyl radicals, strong oxidants that can degrade organic compounds via hydrogen abstraction. AFT has potential use for the remediation of aqueous pesticide waste. The degradation rates of chloroacetanilides by AFT were investigated in this work, which demonstrates that AFT can be used to rapidly and completely remove chloroacetanilide herbicides from aqueous solutions. Acetochlor, alachlor, butachlor, metolachlor, and propachlor were treated by AFT, and parent compound concentrations were analyzed over the course of the treatment time. Degradation curves were plotted and fitted by the AFT kinetic model for each herbicide, and AFT model kinetic parameters were used to calculate degradation rate constants. The reactivity order of these five active ingredients toward hydroxyl radical was acetochlor approximately metolachlor > butachlor approximately alachlor > propachlor. Treatment of the chloroacetanilides by AFT removed the parent compounds but did not completely mineralize them. However, AFT did result in an increase in the biodegradability of chloroacetanilide aqueous solutions, as evidenced by an increase in the 5-day biochemical oxygen demand to chemical oxygen demand ratio (BOD5/COD) to >0.3, indicating completely biodegradable solutions. Several degradation products were formed and subsequently degraded, although not always completely. Some of these were identified by mass spectral analyses. Among the products, isomers of phenolic and carbonyl derivatives of parent compounds were common to each of the herbicides analyzed. More extensively oxidized products were not detected. Degradation pathways are proposed for each of the parent compounds and identified products.

Kinetic Effect of Humic Acid on Alachlor Degradation by Anodic Fenton Treatment

Contamination of water often results from the heavy use of agricultural chemicals, and the disposal of aqueous pesticide waste is a concern. Anodic Fenton treatment (AFT) has been shown to be a successful remediation method for pesticides in solution, but the effect of soil on the degradation kinetics of pesticides using this method has not been determined. The purpose of this study was to study the effect of humic acid, as a soil surrogate, on the degradation kinetics of alachlor [2-chloro-N-(2,6-diethylphenyl-N-(methoxymethyl) acetamide], a heavily used herbicide that has been studied in pure aqueous solution by AFT. The AFT consists of a controlled constant delivery of Fenton reagents, using an electrochemical half-cell to deliver ferrous iron. Alachlor was quickly degraded by AFT, and the kinetics were found to obey the previously developed AFT model well. Degradation of alachlor by AFT in humic acid slurry showed that when the amount of humic acid was increased, alachlor degradation was significantly slowed down and the degradation kinetics were shifted from the AFT model to a first-order model. Further experimentation indicated that humic acid not only competes with alachlor for hydroxyl radicals, reducing the degradation rate of the target compound, but also buffers the slurry at near neutral pH, blocking regeneration of ferrous ion from ferric ion and subsequently shifting the kinetics to first order. Degradation of several other pesticides in humic acid slurry also followed first-order kinetics. These results imply that higher concentrations of Fenton reagents will be required for soil remediation.

The binary treatment of aqueous metribuzin using anodic fenton treatment and biodegradation.

An advanced oxidation process, anodic Fenton treatment (AFT), and a mixed microbial culture were used to degrade metribuzin [4-amino-6-tert-butyl-3-methylthio-1,2,4- triazin-5(4H)-one], a broad-use triazinone herbicide. Complete and rapid removal of metribuzin was demonstrated. The appearance and subsequent degradation of metribuzin oxidation products--deaminated metribuzin (DA), diketo metribuzin (DK), as well as the production of deaminated diketo metribuzin (DADK)--were observed. To support the use of AFT as a chemical pretreatment, the ratio of 5-day biochemical oxygen demand (BOD5) as measured in the standard test to chemical oxygen demand (COD) was investigated, and an increase from 0.03, a nonbiodegradable solution, to 0.35, a biodegradable solution, was observed. This increase in biodegradability was associated with decreased metribuzin, DA, and DK concentrations and increased DADK concentration. AFT effluent was inoculated with either an enriched microbial culture or Polyseed, a commercially available inoculum. Although there was minimal biodegradation of the remaining metribuzin, there was a significant decrease in DA concentration in inoculated incubations compared with sterile controls after 5- and 10-minute AFT treatment. The enrichment inoculate appeared more adapted toward the less-oxidized, 5-minute-treated effluent, whereas the Polyseed culture, developed to degrade complex waste solutions, appeared to be more effective in a moreoxidized, 10-minute-treated, and potentially more complex effluent. This research supports the continued investigation of AFT and biodegradation as a binary treatment of aqueous pesticide wastes.

Metribuzin Degradation by Membrane Anodic Fenton Treatment and Its Interaction with Ferric Ion

Metribuzin, a widely used herbicide and a frequently detected pollutant in the environment, was studied as a target compound for membrane anodic Fenton treatment (AFT), a Fenton technology with application potential for on-site treatment of pesticide wastewater. It was found that the degradation kinetics of metribuzin do not obey the AFT model, a previously developed model that fit AFT degradation kinetics of all previously investigated pesticides. The lack of fit for metribuzin data was determined to result from a weak interaction between metribuzin and the ferric ion, resulting in a significant reduction in availability of metribuzin for reaction with hydroxyl radicals during AFT, thus slowing degradation. A revised kinetic model was developed based on the original AFT model with the addition of this interaction. Results demonstrate that the new kinetic model fits metribuzin degradation data quite well at different delivery rates of Fenton reagent and at different temperatures. This weak interaction is also found to exist between ferric ion and several other triazinone/triazine herbicides during membrane AFT. The interaction intensity correlates with the electron-withdrawing/-donating property of substituents on the triazine/triazinone ring. The stronger the electron-donating ability of substituents, the stronger the interaction.

Competitive degradation and detoxification of carbamate insecticides by membrane anodic Fenton treatment.

The competitive degradation of six carbamate insecticides by membrane anodic Fenton treatment (AFT), a new Fenton treatment technology, was carried out in this study. The carbamates studied were dioxacarb, carbaryl, fenobucarb, promecarb, bendiocarb, and carbofuran. The results indicate that AFT can effectively degrade these insecticides in both single component and multicomponent systems. The carbamates compete for hydroxyl radicals, and their kinetics obey the previously developed AFT kinetic model quite well. Hydroxyl radical reaction rate constants were obtained, and they decrease in the following order: dioxacarb approximately carbaryl > fenobucarb > promecarb > bendiocarb > carbofuran. The AFT is shown to have higher treatment efficiency at higher temperature. Degradation products of the carbamates were determined by gas chromatography/mass spectrometry, and it appears that degradation can be initiated by hydroxyl radical attack at different sites in the molecule, depending on the individual structure of the compound. Substituted phenols are the commonly seen degradation products. The AFT treatment can efficiently remove the chemical oxygen demand of the carbamate mixture, significantly increasing the biodegradability. Earthworm studies show that the AFT is also an effective detoxification process.

Oxidative degradation and detoxification of aqueous carbofuran by membrane anodic Fenton treatment

Anodic Fenton treatment (AFT), a new Fenton technology for the treatment of pesticide wastewater, has been reported previously. The substitution of an ion exchange membrane for the salt-bridge, an improvement to the practicality of the AFT without sacrificing treatment efficiency, has also been reported. The oxidative degradation by membrane AFT of carbofuran, a heavily used and toxic carbamate insecticide, was investigated in this study. The results show that the degradation kinetics of carbofuran with different initial concentrations obeys the AFT model, and the treatment efficiency increases with increasing initial concentration. Raising the treatment temperature can result in enhanced degradation of carbofuran in solution. The pseudo-activation energy of carbofuran by membrane AFT was estimated to be 7.66 kJ mol −1. The results also show that AFT treatment can effectively remove COD and dramatically improve the biodegradability of carbofuran in solution. GC/MS analysis found four degradation products, revealing that the carbamate branch and 3-C in the furan ring are the first and second attack targets of hydroxyl radicals. As shown by the toxicity assay, the fatal toxicity of carbofuran to earthworms can be totally removed. The degradation of carbofuran by AFT is also a detoxification process.