Efficient removal of insecticide “imidacloprid” from water by electrochemical advanced oxidation processes

The oxidative degradation of imidacloprid (ICP) has been carried out by electrochemical advanced oxidation processes (EAOPs), anodic oxidation, and electro-Fenton, in which hydroxyl radicals are generated electrocatalytically. Carbon-felt cathode and platinum or boron-doped diamond (BDD) anodes were used in electrolysis cell. To determine optimum operating conditions, the effects of applied current and catalyst concentration were investigated. The decay of ICP during the oxidative degradation was well fitted to pseudo-first-order reaction kinetics and absolute rate constant of the oxidation of ICP by hydroxyl radicals was found to be k _abs(ICP)?=?1.23?×?10⁹ L mol^?1 s^?1. The results showed that both anodic oxidation and electro-Fenton process with BDD anode exhibited high mineralization efficiency reaching 91 and 94 % total organic carbon (TOC) removal at 2 h, respectively. For Pt-EF process, mineralization efficiency was also obtained as 71 %. The degradation products of ICP were identified and a plausible general oxidation mechanism was proposed. Some of the main reaction intermediates such as 6-chloronicotinic acid, 6-chloronicotinaldehyde, and 6-hydroxynicotinic acid were determined by GC-MS analysis. Before complete mineralization, formic, acetic, oxalic, and glyoxylic acids were identified as end-products. The initial chlorine and organic nitrogen present in ICP were found to be converted to inorganic anions Cl^?, NO₃ ^?, and NH₄ ⁺.     

Comparison of various advanced oxidation processes for the degradation of phenylurea herbicides

Various types of advanced oxidation processes (AOPs), such as UV photolysis, ozonation, heterogeneous photocatalysis and their combinations were comparatively examined at the same energy input in a home-made reactor. The oxidative transformations of the phenylurea herbicides fenuron, monuron and diuron were investigated. The initial rates of transformation demonstrated that UV photolysis was highly efficient in the cases of diuron and monuron. Ozonation proved to be much more effective in the transformation of fenuron than in those of the chlorine containing monuron and diuron. In heterogeneous photocatalysis, the rate of decomposition decreased with increase of the number of chlorine atoms in the target molecule. Addition of ozone to UV-irradiated solutions and/or TiO₂-containing suspensions markedly increased the initial rates of degradation. Dehalogenation of monuron and diuron showed that each of these procedures is suitable for the simultaneous removal of chlorinated pesticides and their chlorinated intermediates. Heterogeneous photocatalysis was found to be effective in the mineralization.     

Fenton-like degradation of nalidixic acid with Fe3+/H2O2

The Fenton-like degradation of nalidixic acid was studied in this work. The effects of Fe³⁺ concentration and initial H₂O₂ concentration were investigated. Increasing the initial H₂O₂ concentration enhances the degradation and mineralization efficiency for nalidixic acid, while Fe³⁺ shows an optimal concentration of 0.25 mM. A complete removal of nalidixic acid and a TOC removal of 28 % were achieved in 60 min under a reaction condition of [Fe³⁺]?=?0.25 mM, [H₂O₂]?=?10 mM, T?=?35 °C, and pH?=?3. LC–MS analysis technique was used to analyze the possible degradation intermediates. The degradation pathways of nalidixic acid were proposed according to the identified intermediates and the electron density distribution of nalidixic acid. The Fenton-like degradation reaction of nalidixic acid mainly begins with the electrophilic attack of hydroxyl radical towards the C₃ position which results in the ring-opening reaction; meanwhile, hydroxyl radical attacking to the branched alkyl groups of nalidixic acid leads to the oxidation at the branched alkyl groups.     

Phenol electrooxidation on Fe-Co3O4 thin film electrodes in alkaline medium

Fe-Co₃O₄ thin film with different amounts of Fe have been used for the electro-oxidation of phenol in alkaline medium at room temperature. The electrodes were prepared by coating stainless steel supports with successive layers of the oxides, obtained by thermal decomposition at 673 K. The electrolysis was carried out at constant potential and the phenol disappearance, during the electrolysis, was monitored by UV-Vis absorbance measurements between 250 and 500 nm. After 3 h of electrolysis, the intermediates were identified by comparing the HPLC data and UV-Vis spectra to those from pure standards. The results indicate that the same oxidation products are formed on the different prepared electrodes, namely the decomposition products of phenol such as benzoquinone, hydroquinone and cathecol in basic medium. Simulated results show clearly the decrease of the amount of phenolic species with the electrolysis time. An enhancement of the phenol removal is observed with the presence of iron in the oxide. Under the operating conditions, around 30% of the initial phenol has been removed at ca. 3 h and the complete degradation is obtained after 54 h of electrolysis, when Fe-Co₃O₄ thin film with 10% of Fe is used as anode.     

Photocatalytic decomposition of crotamiton over aqueous TiO(2) suspensions: determination of intermediates and the reaction pathway

The photocatalytic degradation of crotamiton in aqueous solution using TiO₂ was investigated. To investigate the effect of initial pH, the photodegradation behaviors of three types of pharmaceuticals were compared (crotamiton, clofibric acid, sulfamethoxazole). The degradation rates of crotamiton in the pH range 3-9 were nearly equal, but those of clofibric acid and sulfamethoxazole were affected by pH. At pH > 6.5, TiO₂ particles, clofibric acid and sulfamethoxazole had negative charge, therefore, the repulsive force between TiO₂ particles and anionic pharmaceuticals occurred and a low reaction rate at high pH was observed. The effect of UV intensity and TiO₂ concentration on photodegradation efficiency was also investigated. Linear and logarithmical relationships between UV intensity, TiO₂ concentration and the reaction rate constant were confirmed. Furthermore, the structures of photodegradation intermediates formed concomitantly with the disappearance of crotamiton were estimated. Seven intermediates were characterized by LC/MS/MS analyses, and it was assumed that the photocatalytic degradation of crotamiton was initiated by the attack of electrophilic hydroxyl radicals on aromatic rings and alkyl chains.     

Ce-PbO2/C电极的制备及其去除水中酸性红B

采用电沉积法制备铈修饰的PbO2/C电极,通过SEM、XRD、XPS及循环伏安对PbO2/C、Ce-PbO2/C电极进行表征,结果表明,Ce-PbO2/C电极比PbO2/C颗粒细小,表面均匀致密,电化学氧化能力较强,修饰电极中Ce以CeO2的形态存在。以Ce-PbO2/C为工作电极,电解浓度为1 000 mg/L的高盐酸性红B模拟活性染料废水,考察了电压、pH、电解质浓度、极间距对脱色率、氨氮去除率及COD去除率的影响。确定适宜工艺条件为:初始酸性红B溶液浓度为1 000 mg/L,pH值为6,电压10 V,电解时间1 h,电极间距1.5 cm,该条件下脱色率、氨氮去除率和COD去除率分别为99.98%、97.23%和90.17%。通过UV-Vis及GC-MS初步分析了降解过程可能存在的中间产物及降解途径。     

臭氧氧化及其他强化技术协同降解聚乙烯醇

采用O₃氧化降解水中聚乙烯醇（PVA）,考察了O₃氧化的影响因素及与其他强化技术协同下的降解效果。结果表明,经12 min处理,O₃/超声波、O₃/紫外光协同作用下PVA降解率较直接O₃氧化的63.2%有显著提高,表现出了良好的协同效应。通过比较酸性条件下添加不同量Fenton试剂的作用效果可知,·OH的氧化作用是PVA降解的重要原因。     

Electro-Fenton degradation of the antibiotic sulfanilamide with Pt/carbon-felt and BDD/carbon-felt cells. Kinetics,reaction intermediates,and toxicity assessment

The degradation of 230 mL of a 0.6-mM sulfanilamide solution in 0.05 M Na₂SO₄ of pH 3.0 has been studied by electro-Fenton process. The electrolytic cell contained either a Pt or boron-doped diamond (BDD) anode and a carbon-felt cathode. Under these conditions, organics are oxidized by hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton’s reaction between initially added (and then electrochemically regenerated) Fe²⁺ and cathodically generated H₂O₂. From the decay of sulfanilamide concentration determined by reversed-phase liquid chromatography, an optimum Fe²⁺ concentration of 0.20 mM in both cells was found. The drug disappeared more rapidly using BDD than Pt, and, in both cases, it was more quickly removed with raising applied current. Almost total mineralization was achieved using the BDD/carbon-felt cell, whereas the alternative use of Pt anode led to a slightly lower mineralization degree. In both cells, the degradation rate was accelerated at higher current but with the concomitant fall of mineralization current efficiency due to the greater increase in rate of the parasitic reactions of hydroxyl radicals. Reversed-phase liquid chromatography allowed the identification of catechol, resorcinol, hydroquinone, p-benzoquinone, and 1,2,4-trihydroxybenzene as aromatic intermediates, whereas ion exclusion chromatography revealed the formation of malic, maleic, fumaric, acetic, oxalic, formic, and oxamic acids. NH₄ ⁺, NO₃ ^?, and SO₄ ^2? ions were released during the electro-Fenton process. A plausible reaction sequence for sulfanilamide mineralization involving all detected intermediates has been proposed. The toxicity of the solution was assessed from the Vibrio fischeri bacteria luminescence inhibition. Although it acquired its maximum value at short electrolysis time, the solution was completely detoxified at the end of the electro-Fenton treatment, regardless of the anode used.     

Remediation of 4-nonylphenol in aqueous solution by using free radicals generated by the oxidative reactions

Introduction

This study relates to use of zerovalent iron to generate hydroxyl free radicals and undergo subsequent oxidation to destroy 4-nonylphenol (NP) by mild process in aqueous solution and activation of oxygen gas (O₂) at room temperature. This technology is based on a novel oxidative mechanism mediated by zerovalent iron rather than commonly used reduction mechanism.

Materials and methods

A laboratory scale device consisting of a 250?ml pyrex serum vials fixed to a Vortex agitator was used. Different amounts of zerovalent iron powder (ZVI; 1, 10, and 30?g/l) at pH?4 and room temperature with bubbling of oxygen gas were investigated.

Results and conclusion

Experiments showed an observed degradation rate k _(obs) directly proportional to the amount of iron. 4-Nonylphenol degradation reactions demonstrated first-order kinetics with a half-life of about 10.5?±?0.5 and 3.5?±?0.2?min when experiments were conducted at [ZVI]?=?1 and 30?g/l respectively. Three analytical techniques were employed to monitor 4-nonylphenol degradation and mineralization: (1) spectrofluorimetry; (2) high-performance liquid chromatography; (3) total organic carbon meter (TOC meter). Results showed a complete disappearance of 4-nonylphenol after 20?min of contact with ZVI. The intermediate by-products of the reaction were not identified but the disappearance of NP was monitored by the three above-mentioned techniques.     

MnO2催化Fenton试剂降解苯酚废水

实验对MnO2催化Fenton试剂氧化高浓度苯酚废水的动力学特性和去除效果进行了研究。结果表明,MnO2可以提高Fenton试剂体系对苯酚的降解率以及COD的去除率;Fenton试剂以及MnO2催化Fenton试剂氧化苯酚废水体系中苯酚的降解都符合拟一级动力学模型。在MnO2催化Fenton试剂氧化体系中,苯酚的降解速率常数有明显提高,反应活化能也有所降低,说明MnO2的加入可以使反应容易进行。废水降解前后紫外可见吸收光谱和红外谱图表明,Fenton试剂法将苯酚可能降解为羧酸、烯烃等有机物中间体。     

Photocatalytic removal of organic pollutants in aqueous solution by Bi(4)Nb(x)Ta((1-x))O(8)I

In this work, Bi₄Nb_xTa_(1−x)O₈I photocatalysts have been synthesized by solid state reaction method and characterized by powder X-ray diffraction, scanning electron microscope and UV-Vis near infrared diffuse reflectance spectroscopy. The photocatalytic activity of these photocatalysts was evaluated by the degradation of methyl orange (MO) in aqueous solutions under visible light, UV light and solar irradiation. The effects of catalyst dosage, initial pH and MO concentration on the removal efficiency were studied, and the photocatalytic reaction kinetics of MO degradation as well. The results indicated that Bi₄Nb_xTa_(1−x)O₈I exhibited high photocatalytic activity for the removal of MO in aqueous solutions. For example, the removal efficiency of MO by Bi₄Nb_0.1Ta_0.9O₈I was as high as 92% within 12 h visible light irradiation under the optimal conditions: initial MO concentration of 5-10 mg L⁻¹, catalyst dosage of 6 g L⁻¹ and natural pH (6-8), the MO molecules could be completely degradated by Bi₄Nb_0.1Ta_0.9O₈I within 40 min under UV light irradiation, and the photodegradation efficiency reaches to 60% after 7 h solar irradiation. Furthermore, the photocatalytic degradation of Bisphenol A (BPA) was also investigated under visible light irradiation. It is found that 99% BPA could be mineralized by Bi₄Nb_0.1Ta_0.9O₈I after 16 h visible light irradiation. Through HPLC/MS, BOD, TOC, UV-Vis measurements, we determined possible degradation products of MO and BPA. The results indicated that MO was degradated into products which are easier to be biodegradable and innocuous treated, and BPA could be mineralized completely. Furthermore, the possibility for the photosensitization effect in the degradation process of MO under visible light irradiation has been excluded.     

Oxidation of ofloxacin by Oxone/Co2+: identification of reaction products and pathways

Oxidative degradation of ofloxacin (OFX) by sulfate free radicals (SO₄ ^??) in the UV/Oxone/Co²⁺oxidation process was investigated for the first time, with a special focus upon identifying the transformation products as well as understanding the reaction pathways. Thirteen main compounds were identified after the initial transformation of OFX; the detailed structural information of which were characterized by high-performance liquid chromatography–high resolution mass spectrometry and MS fragmentation analysis. The degradation pathways mainly encompassed ring openings at both the piperazinyl substituent and the quinolone moiety, indicating that the usage of SO₄ ^?? aided the oxidative degradation of OFX to undergo more facile routes compared to those in previous reports by using OH^?/h⁺ as the oxidant, where the initial transformation attacks were mainly confined to the piperazine moiety. Moreover, in this study, smart control over the pH conditions of the oxidation system via different modes of Oxone dosage resulted in the selective degradation of the functional sites of OFX molecule, where it was shown that the SO₄ ^??-driven destruction of the quinolone moiety of OFX molecule favored the neutral pH conditions. This would be beneficial for the reduction of bacterial resistance against quinolones in the aqueous environment.     

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.     

Degradation of rhodamine B by Fe(0)-based Fenton process with H2O2

Degradation of rhodamine B by Fe(0)-based Fenton process with H₂O₂ was investigated. The effects of H₂O₂ dose, Fe(0) dose, initial concentration of rhodamine B and initial pH value on the degradation of rhodamine B were examined. The results showed that the degradation and mineralization of rhodamine B occurred with low dose of H₂O₂ and Fe(0). The intermediates of rhodamine B were analyzed with UV-Vis spectrophotometry and ion chromatography and the mechanism of oxidative degradation of rhodamine B was also discussed. The reactive oxygen species (·OH) produced in Fe(0)-based Fenton process with H₂O₂ is the key to the degradation of rhodamine B by ways of N-de-ethylation, chromophore cleavage, ring-opening and mineralization.     

Heterogeneous reactions of suspended parathion, malathion, and fenthion particles with NO(3) radicals

Organophosphorus pesticides (OPPs) emit into the atmosphere in both gas and particulate phases via spray drift from treatments and post-application emission, but most of their degradations in the atmosphere are not well known. In this study, the heterogeneous reactions of nitrate (NO₃) radicals with three typical OPPs (parathion, malathion, and fenthion) absorbed on azelaic acid particles are investigated using an online vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). The reaction products observed with the VUV-ATOFMS are identified on the basis of GC/MS analysis of the products in the reaction between NO₃ radicals and the coating of the pesticide. Paraoxon is identified as the only product of parathion; malaoxon and bis(1,2-bis-ethoxycarbonylethyl)disulfide as the products of malathion; fenoxon, fenoxon sulfoxide, fenthion sulfoxide, fenoxon sulfone, and fenthion sulfone as the products of fenthion. The degradation rates of parathion, malathion, and fenthion under the experimental conditions are 5.5 × 10⁻³, 5.6 × 10⁻², and 3.3 × 10⁻² s⁻¹, respectively. The pathways of the heterogeneous reactions between the three OPPs and NO₃ radicals are proposed. The experimental results reveal the possible transformations of these OPPs through the oxidation of NO₃ radicals in the atmosphere.     

Degradation of diethyl phthalate (DEP) by vacuum ultraviolet process: influencing factors,oxidation products,and toxicity assessment

The vacuum ultraviolet (VUV) process, which can directly produce hydroxyl radical from water, is considered to be a promising oxidation process in degrading contaminants of emerging concern, because of no need for extra reagents. In this study, the influencing factors and mechanism for degradation of diethyl phthalate (DEP) by the VUV process were investigated. The effects of irradiation intensity, inorganic anions, natural organic matter (NOM), and H₂O₂ dosage on the performance of VUV process were evaluated. The results showed that DEP could be more efficiently degraded by the VUV process compared with ultraviolet (UV)-254-nm irradiation. The presence of HCO₃^?, NO₃^? and NOM in the aqueous solutions inhibited the degradation of DEP to a different degree, mainly by competing hydroxyl radicals (HO^?) with DEP. Degradation rate and removal efficiency of DEP by VUV process significantly enhanced with the addition of H₂O₂, while excess H₂O₂ dosage could inhibit the DEP degradation. Moreover, based on the identified seven oxidation byproducts and their time-dependent evolution profiles, a possible pathway for DEP degradation during the VUV process was proposed. Finally, the ecotoxicity of DEP and its oxidation byproducts reduced overall according to the calculated results from Ecological Structure Activity Relationships (ECOSAR) program. The electrical energy per order (EE/O) was also assessed to analysis the energy cost of the DEP degradation in the VUV process. Our work showed the VUV process could be an alternative and environmental friendly technology for removing contaminants in water.

     

The effect of O2 and NO2 on the ring retaining products of the reaction of toluene with hydroxyl radicals

The reaction of toluene with hydroxyl radicals produces ring retaining products either from H-atom abstraction from the methyl group: benzaldehyde and benzylalcohol or from the addition of the hydroxyl radical to the aromatic ring: o-, m+p-cresol. The yields obtained in experiments carried out in nitrogen and in air matrix were statistically not significantly different. The addition of NO₂ to the reactants had no effect on the formed o-cresol, indicating that reaction of the hydroxy-methylcyclohexadienyl radical with NO₂ is not contributing significantly to the formation of o-cresol. This is in agreement with recent studies postulating the more stable toluene oxide as the intermediate resulting from the reaction of hydroxy-methylcyclohexadienyl with oxygen rather than the peroxy radical. m-nitrotoluene was the major nitrotoluene formed in the presence of NO₂, increasing linearly with increasing the initial concentration of NO₂ with zero intercept. The observed 2-methyl 1,4 benzoquinone and traces of phenol and benzene were determined to be secondary products.     

Electro-oxidation of the dye azure B: kinetics,mechanism, and by-products

In this work, the electrochemical degradation of the dye azure B in aqueous solutions was studied by electrochemical advanced oxidation processes (EAOPs), electro-Fenton, and anodic oxidation processes, using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with H₂O₂ electrogeneration. The higher oxidation power of the electro-Fenton (EF) process using BDD anode was demonstrated. The oxidative degradation of azure B by the electrochemically generated hydroxyl radicals (^?OH) follows a pseudo-first-order kinetics. The apparent rate constants of the oxidation of azure B by ^?OH were measured according to pseudo-first-order kinetic model. The absolute rate constant of azure B hydroxylation reaction was determined by competition kinetics method and found to be 1.19?×?10⁹ M^?1 s^?1. It was found that the electrochemical degradation of the dye leads to the formation of aromatic by-products which are then oxidized to aliphatic carboxylic acids before their almost mineralization to CO₂ and inorganic ions (sulfate, nitrate, and ammonium). The evolution of the TOC removal and time course of short-chain carboxylic acids during treatment were also investigated.     

Photocatalytic degradation of the herbicide pendimethalin using nanoparticles of BaTiO3/TiO2 prepared by gel to crystalline conversion method: A kinetic approach

Photocatalytic degradation of the herbicide, pendimethalin (PM) was investigated with BaTiO₃/TiO₂ UV light system in the presence of peroxide and persulphate species in aqueous medium. The nanoparticles of BaTiO₃ and TiO₂ were obtained by gel to crystallite conversion method. These photo catalysts are characterized by energy dispersive x-ray analysis (EDX), scanning electron microscope (SEM), x-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) adsorption isotherm and reflectance spectral studies. The quantum yields for TiO₂ and BaTiO₃ for the degradation reactions are 3.166 Einstein m^?2 s^?1 and 2.729 Einstein m^?2 s^?1 and catalytic efficiencies are 6.0444 × 10^?7 mg^?2h^?1L² and 5.403 × 10^?7 mg^?2h^?1L², respectively as calculated from experimental results. BaTiO₃ exhibited comparable photocatalytic efficiency in the degradation of pendimethalin as the most widely used TiO₂ photocatalyst. The persulphate played an important role in enhancing the rate of degradation of pendimethalin when compared to hydrogen peroxide. The degradation process of pendimethalin followed the first-order kinetics and it is in agreement with Langmuir-Hinshelwood model of surface mechanism. The reason for high stability of pendimethalin for UV-degradation even in the presence of catalyst and oxidizing agents were explored. The higher rate of degradation was observed in alkaline medium at pH 11. The degradation process was monitored by spectroscopic techniques such as ultra violet-visible (UV-Vis), infrared (IR) and gas chromatography mass spectroscopy (GC-MS). The major intermediate products identified were: N-propyl-2-nitro-6-amino-3, 4-xylidine, (2, 3-dimethyl-5-nitro-6-hydroxy amine) phenol and N-Propyl-3, 4-dimethyl-2, 6-dinitroaniline by GC-MS analysis and the probable reaction mechanism has been proposed based on these products.