Research Note : Removal of Atrazine by Ozone and Ozone-Hydrogen Peroxide Combinations in Surface Water

Atrazine is one of the most frequently identified pesticides in Europe. Current European standards stipulate that the maximum contaminant level (MCL) for the individual pesticide is 100 ng/L. This regulation stresses the need for a low-cost and effective treatment system. Adsorption is one promising solution, but, in general, breakthrough of the granular activated carbon filter occurs rapidly. Recent research has shown that ozonation alone utilized according to the usual practical conditions removes atrazine only poorly (15-25%). High oxidation reaction rates of the hydroxyl free radical suggest a better, removal method by combinations of O₃/H₂O₂. The feasibility of such a combination has been evaluated in this present study.     

Ozone Oxidation of Endocrine Disruptors and Pharmaceuticals in Surface Water and Wastewater

The oxidative removal of a diverse group of trace organic contaminants from surface water and wastewater was evaluated using ozone (O₃) and O₃ combined with hydrogen peroxide (O₃/H₂O₂). Target compounds included estrogenic and androgenic steroids, pharmaceuticals, pesticides, and industrial chemicals. Bench- and pilot- scale experiments were conducted with surface water spiked with the target compounds and wastewater effluent containing ambient concentrations of target compounds. Full-scale water treatment plants were sampled before and after ozonation to determine if bench- and pilot-scale results accurately predict full-scale removal. In both drinking water and wastewater experiments, the majority of target compounds were removed by greater than 90% at O₃ exposures commonly used for disinfection. Atrazine, iopromide, meprobamate, and tris-chloroethylphosphate (TCEP) were the most recalcitrant compounds to oxidize using O₃, with removals generally less than 50%. The addition of H₂O₂ for advanced oxidation was of little benefit for contaminant removal as compared to O₃ alone. O₃/H₂O₂ provided a marginal increase in the removal of dilantin, diazepam, DEET, iopromide, and meprobamate, while decreasing the removal efficacy of pentoxifylline, caffeine, testosterone, progesterone, and androstenedione. In wastewater experiments, O₃ and O₃/H₂O₂ were shown to remove in vitro estrogenicity. Collectively, these data provide evidence that O₃ is a highly effective oxidant for removing the majority of trace organic contaminants from water.     

Fenton-driven regeneration of MTBE-spent granular activated carbon—Effects of particle size and iron amendment procedures

Fenton-driven regeneration of spent granular activated carbon (GAC) can be used to regenerate organic contaminant-spent GAC. In this study, the effects of GAC particle size (>2 mm to <0.35 mm) and acid pre-treatment of GAC on Fenton-driven oxidation of methyl-tert-butyl ether (MTBE)-spent GAC were evaluated. Iron (Fe) was amended to the GAC using two methods: (1) untreated—where GAC was amended with a concentrated solution of ferrous sulfate and (2) acid pre-treatment—where GAC was amended with acid followed by sequential applications of a dilute ferrous sulfate solution. Subsequently, MTBE was amended to the GAC, followed by oxidative treatments with H₂O₂. H₂O₂ reaction and MTBE oxidation were inversely correlated with GAC particle size and were attributed to shorter intraparticle diffusion transport distances for both H₂O₂ and MTBE. Image analysis of the GAC cross-sections (i.e., prepared thin sections) revealed that the Fe amended to the GAC extended to the center of the GAC particles. Fe accumulated at higher levels on the periphery of the untreated GAC but Fe dispersal was more uniform in the acid pre-treated GAC. In the acid pre-treated GAC, conditions for MTBE oxidation were favorable and greater levels of MTBE oxidation were measured for all particle size fractions tested. Modeling and critical analysis of H₂O₂ diffusive transport and reaction indicated limited H₂O₂ penetration into large GAC particles which contributed to a decline in MTBE removal. Residual MTBE remaining on the GAC limited the quantity of MTBE that could be re-adsorbed, but no reduction in MTBE sorption capacity resulted from oxidative treatments.     

Reduction of Biocide-Polluted Wastewater Using O3 and H2O2/O3 Oxidation Processes

The objective of the presented study was to test various oxidation processes with the aim being to reduce the concentration and toxicity of biocide wastewater from a Slovenian phytopharmaceutical factory. Laboratory-scale experiments employing two AOP processes – ozonation (O₃) and peroxone (H₂O₂/O₃) – were applied to reduce the concentration of the active components involved, i.e., methylisothiazolone (MI), chloromethylisothiazolone (CMI) and dichloromethylisothiazolone (DCMI). The reduction of the biocide wastewater load for the performed oxidation processes was evaluated using ecological parameters. The H₂O₂/O₃ oxidation procedure using an O₃ flow rate of 1g/L h, at a pH value of 10 and with the addition of 5 ml of H₂O₂ (0.3 M) proved to be the most effective treatment. The toxicity of the biocide-load wastewater with an initial EC₅₀ = 0.38%, decreased to EC₅₀ (24h) >100% and EC₅₀ (48h) = 76%.     

Comparison of Hydroxyl Radical Generation for Various Advanced Oxidation Combinations as Applied to Foundries

The authors monitored hydrogen peroxide (H₂O₂), ozone (O₃), and apparent hydroxyl radical (OH·) concentrations in the liquid phase, along with gas phase ozone when operating an advanced oxidation (AO) system that included H₂O₂, O₃, sonication, and underwater plasma (UWAP). The OH· radical converted non-fluorescent terephthalic acid to fluorescent hydroxyterephthalic acid (HTA). As determined from HTA formation, when a 500 ppm H₂O₂ dose in tap water was combined with O₃ and sonication, nearly twice as much OH· (0.72 ppm) accumulated than with H₂O₂ alone. When UWAP accompanied H₂O₂, O₃, and sonication, these together generated 15–35% more OH· than when UWAP was excluded. When ozone was introduced into this AO system, the AO system decomposed almost all the O₃. This research has been conducted as a part of a study that has appraised this advanced oxidation system (Sonoperoxone) in green sand foundries, where it has diminished volatile organic compound (VOC) and hazardous air pollutant (HAP) emissions by 20–75%; and clay and coal consumption by 20–35%.     

Oxidation of Parachloronitrobenzene in Dilute Aqueous Solution by O3 + UV and H2O2 + UV : A Comparative Study

This laboratory study was designed to investigate the degradation of 4-chloronitrobenzene ([CNB] = 2.4 × 10^?6 mol L^?1; pH = 7.5) by H₂O₂/UV and by O₃/UV oxidation processes which involve the generation of very reactive and oxidizing hydroxyl free radicals. The effects of the oxidant doses (H₂O₂ or aqueous O₃), liquid flow rate (or the contact time), and bicarbonate ions acting as OH· radical scavengers on the CNB removal rates were studied. For a constant oxidant dose, the results show that the O₃/UV system appears to be more efficient than the H₂O₂/UV system to remove CNB because of the greatest rate of OH· generation by ozone photodecomposition compared to H₂O₂ photolysis. However, for a given amount of oxidant decomposed, the H₂O₂/UV oxidant system was found to be more efficient than O₃/UV. Moreover, high levels of bicarbonate ions in solution (4 × 10^?3 mol L^?1) significantly decrease the efficiency of CNB removal by H₂O₂/UV and by O₃/UV oxidation processes.     

Oxidation of cyclopentene catalyzed by phosphotungstic quaternary ammonium salt catalysts

A series of phosphotungstic quaternary ammonium salts, Q₃ (PW₁₂O₄₀) and Q₃(PW₄O₁₆) [Q = (C₅H₅)N⁺(C₁₆H₃₃), (C₁₆H₃₃)N⁺(CH₃)₃, (C₄H₉)₄N⁺, and (CH₃)₄N⁺], were used as the catalysts in oxidation of cyclopentene. The catalysts [(C₅H₅)N(C₁₆H₃₃)]₃(PW₄O₁₆) and [(C₁₆H₃₃)N(CH₃)₃]₃(PW₄O₁₆) showed high catalytic activity in the selective oxidation of cyclopentene while using H₂O₂ (50%) as an oxidant and 2-propanol as a solvent. The oxidation products mainly consisted of glutaraldehyde, cis-1,2-cyclopentanediol and trans-1,2-cyclopentanediol. The above-mentioned two catalysts were dissolved completely in the reaction medium during the catalysis process and precipitated themselves from the reaction system after reaction, showing the characteristics of reaction-controlled phase-transfer catalysis. The types of quaternary ammonium cations and the phosphotungstic anions in phosphotungstic quaternary ammonium salts affected catalytic activity.     

Surface properties of self-assembled monolayer films of tetra-substituted cobalt, iron and manganese alkylthio phthalocyanine complexes

Self-assembled monolayer (SAM) films of iron (SAM-1), cobalt (SAM-2) and manganese (SAM-3) phthalocyanine complexes, tetra-substituted with diethylaminoethanethio at the non-peripheral positions, were formed on gold electrode in dimethylformamide (DMF). Electrochemical, impedimentary and surface properties of the SAM films were investigated. Cyclic voltammetry was used to investigate the electrochemical properties of the films. Ability of the films to inhibit common faradaic processes on bare gold surface (gold oxidation, solution redox chemistry of [Fe(H₂O)₆]³⁺/[Fe(H₂O)₆]²⁺ and underpotential deposition (UDP) of copper) was investigated. Electrochemical impedance spectroscopy (EIS), using [Fe(CN)₆]^3−/4− redox process as a probe, offered insights into the electrical properties of the films/electrode interfaces. Surface properties of the films were probed using atomic force microscopy (AFM) and scanning electron microscopy (SEM). The films were employed for the electrocatalytic oxidation of the pesticide, carbofuran. Electrocatalysis was evidenced from enhanced current signal and less positive oxidation potential of the pesticide on each film, relative to that observed on the bare gold electrode. Mechanism of electrocatalytic oxidation of the pesticide was studied using rotating disc electrode voltammetry.     

Oxidation of Herbicides in Groundwater by the Fenton Process: A Realistic Alternative for O3/H2O2 Treatment?

Oxidation with O₃/H₂O₂ and Fe²⁺/H₂O₂ are optional for the degradation of herbicides and pesticides in water. The choice of which process will be applied depends upon the degree of degradation of organic micropollutants and the process conditions related to the formation of oxidation by-products, and also on the total costs and the safety and reliability of the process. Under real conditions, atrazine and some phenylureaherbicides were oxidized with O₃/H₂O₂. Comparable experiments under conditions of different pH, iron and DOC content were performed with Fe²⁺/H₂O₂, in order to gain information on the influence of these parameters. The oxidation results of both processes as well as the formation of bromate as one of the oxidation by-products are described. It was found that 80% of atrazine and >99% of some phenylureaherbicides could be degraded with O₃/H₂O₂ at pH 7.8 (H₂O₂/O₃ ratio 3.7 g/g). Under these conditions, bromate was formed up to 5 μg/1. Comparable results were obtained with Fe²⁺/H₂O₂ at a pH value of 5.5, whereas the formation of bromate was kept below 0.2 μg/L.     

Advanced Oxidation of Textile Wastewaters

Model dyeing and laundering wastewaters produced during two basic technological operations of the textile industry were subjected to treatment by advanced oxidation processes (AOPs). The following agents were used: ozone (O₃), hydrogen peroxide (H₂O₂) and UV radiation. They were applied separately and in all possible combinations: O₃ + UV, O₃ + H₂O₂, UV + H₂O₂, as well as all three at the same time: O₃ + UV + H₂O₂. Effluents before and after the treatment were analyzed according to requirements of the Polish Standards that included pH, color threshold, COD and concentration of anionic and non-ionic surfactants. Ozonation was carried out in a lab-scale bubble column reactor with a centrally located UV burner. The most effective version of AOPs proved to be the simultaneous use of all three agents. In the case of such treatment of dyeing wastewaters nearly complete discoloration and full decomposition of surface-active substances were obtained at 80% reduction of COD. A similar tendency was observed in the case of laundering wastewater, though in that case the results were slightly worse, which may be explained by much higher initial concentrations of the pollutants. Good treatment effects have also been obtained in combined treatment by simultaneous use of hydrogen peroxide and ozone.     

Investigation on elemental mercury oxidation mechanism by non-thermal plasma treatment

Converting elemental mercury into divalent compound is one of the most important steps for mercury abatement from coal fired flue gas. The oxidation of elemental mercury was investigated in this paper using dielectric barrier discharge (DBD) non-thermal plasma (NTP) technology at room temperature. Effects of different flue gas components like oxygen, moisture, HCl, NO and SO₂ were investigated. Results indicate that active radicals including O, O₃ and OH all contribute to the oxidation of elemental mercury. Under the conditions of 5% O₂ in the simulated flue gas, about 90.2% of Hg⁰ was observed to be oxidized at 3.68 kV discharge voltage. The increase of discharge voltage, O₂ level and H₂O content can all improve the oxidation rate, individually. With O₂ and H₂O both existed, there is an optimal moisture level for the mercury oxidation during the NTP treatment. In this test, the observed optimal moisture level was around 0.74% by volume. Hydrogen chloride can promote the oxidation of mercury due to chlorine atoms produced in the plasma process. Both NO and SO₂ have inhibitory effects on mercury oxidation, which can be attributed to their competitive consumption of O₃ and O.     

Treatability of Organic Constituents in the Paşaköy Wastewater Treatment Plant Effluent by O3 and O3/H2O2

Effluent from the Pa?aköy Wastewater Treatment Plant was oxidized by using O₃ and O₃/H₂O₂. DOC, COD, UV₂₅₄, total coliform, dissolved ozone and some endocrine disrupting compounds were monitored during oxidation. Results showed that O₃ provided superior disinfection, however, lower reductions in DOC, COD and endocrine disrupting compounds were exhibited compared to O₃/H₂O_2. The highest removal efficiency of DOC, COD and endocrine disrupting compounds were achieved at 0.5 molar ratio of O₃/H₂O_2. The benefit of H₂O₂ addition for advanced oxidation reduced significantly when the mole ratio was increased to 2. Therefore, the mole ratio of H₂O₂ to O₃ is a critical parameter for the design of wastewater oxidation by O₃/H₂O₂.     

Treatment of a mixture of three pesticides by photo- and electro-Fenton processes

In the present work, a comparative study of a mixture of three pesticides (chlortoluron, carbofuran and bentazon) has been investigated by advanced oxidation processes such as photo-Fenton and electro-Fenton. These processes are based on the in situ production of hydroxyl radical, a highly strong oxidant, which allows the degradation of organic pollutants until their mineralization into CO₂ and H₂O. For the photo-Fenton process, the effect of key parameters such as initial catalyst (Fe³⁺) concentration and hydrogen peroxide (H₂O₂) dosage were studied. Under optimal operating conditions, the evolution of total organic carbon (TOC) has been investigated for the two processes. Obtained results showed that more than 90% of TOC removal was obtained after only 2 h of photo-Fenton treatment whereas the electro-Fenton process needed 8 h of treatment. Nevertheless, the comparison of cost treatment shows that the photo-Fenton process is more expensive than electro-Fenton. The evolution of pesticide's concentration during treatment was determined by high performance liquid chromatography (HPLC). Inorganic ions released such as chloride, nitrate, sulphate and ammonium ions are identified and their kinetic evolution was measured by ion chromatographic analyses.     

Evaluation of GO nanosheets decorated by CuFe2O4 and CdS nanoparticles as photocatalyst for the degradation of dinoseb and imidacloprid pesticides

Pesticides are generally utilized one after another for crop conservation, and this pesticide utilization oftentimes resulting in combined pollution of their residues in the environment. An experimental study was performed on the degradation of dinoseb and imidacloprid. In this research, GO/CuFe₂O₄–CdS nanocomposite was synthesized as a high-efficiency photocatalyst for the process of pesticides pollutants from water. Field Emission Scanning Electron Microscopy with Energy Dispersive X-ray (FESEM-EDX), X-Ray Diffraction (XRD), Vibrating-sample Magnetometer (VSM), and Fourier Transform Infrared spectroscopy (FTIR) analyses are applied to study the properties of this nanocomposite. Dinoseb and imidacloprid as pesticide materials have been utilized as water contaminants and their degradation performance using the synthesized photocatalyst is considered. The effect of initial pH, photocatalyst amount, initial pesticide concentration and degradation time are investigated in this research. The optimum values for both pesticides were as follows: pollutant concentration was 10 ppm, the nanocatalyst amount was 100 mg, irradiation time was 100 min and the pH of pesticide solution equaled to 8. The results showed that the GO/CuFe₂O₄–CdS nanocomposite is the efficient nanocatalyst for degradation of these pesticides.     

Effect of magnetic catalysts on the kinetic behaviour of Reactive Black 5 decomposition by an O3/H2O2 process

BACKGROUND: Particles are often too small to be separated from a reaction system and recycled, especially in waste‐water treatment via a catalytic ozonation process. Therefore, the objective of this study was to prepare a magnetic catalyst (SiO₂/Fe₃O₄) that can be recycled by using an external magnetic field. The characteristics of the magnetic catalyst and kinetics of decomposition of Reactive Black 5 (RB5) using a magnetic catalyst/H₂O₂/O₃ have been investigated. Magnetic catalysts (SiO₂/Fe₃O₄) were characterized by X‐ray diffraction (XRD), vibrating sample magnetometry (VSM) and Fourier transform infrared (FTIR) spectroscopy. RESULTS: In the case of the decomposition of RB5 by the SiO₂/Fe₃O₄/H₂O₂/O₃ process, the contribution of the destruction by the indirect oxidation of OH· caused by the chain reaction of H₂O, OH^?, and H₂O₂ was found to be larger than that of the direct attack of O₃. The kinetic behaviour of the reacting species during the decomposition of RB5 by catalytic ozonation could be well modelled under various experimental conditions. CONCLUSIONS: The paramagnetic behaviour of the prepared SiO₂/Fe₃O₄ led to the formation of the magnetic catalyst SiO₂/Fe₃O₄, which could be separated more easily by the application of a magnetic field. More than 90% of the magnetic catalyst was recovered and easily redispersed in a solution for reuse by mixing with a flat‐bladed turbine. Copyright © 2010 Society of Chemical Industry     

Heterogeneously assisted oxidation of adsorbates from carbonmonoxide, methanol and ethanol by hydrogen peroxide solutions on platinum electrodes in sulphuric acid

The influence of hydrogen peroxide on the adsorption and oxidation of carbon monoxide, methanol and ethanol adlayers on porous Pt electrodes were studied in 2 M sulphuric acid solution by means of cyclic voltammetry and differential electrochemical mass spectrometry (DEMS). The oxidation of adsorbed species is observed at electrode potentials far less negative than those required for electrochemical adsorbate oxidation. The oxidation by H₂O₂ is dependent on its concentration in solution, as well as on the adsorbates and their coverages. In all cases the isolated adlayers are oxidised by dissolved H₂O₂. However, the presence of H₂O₂ during adsorption partially inhibits adlayer formation from CH₃OH and C₂H₅OH, but avoids almost completely the adsorption of carbon monoxide. The removal of the residues from the surface by dissolved hydrogen peroxide probably occurs through O_ad species formed during the heterogeneous decomposition reaction of H₂O₂ on Pt.     

Comparison of Ozone and Hydroxyl Radical-Induced Oxidation of Chlorinated Hydrocarbons in Water

The efficiency of ozonation and advanced oxidation processes such as ozone/UV, ozone/H₂O₂ and H₂O₂/UV was assessed for chlorinated hydrocarbons using a closed batch-type system. 1,1-Dichloropropene (DCPE), trichloroethylene (TCE), 1-chloropentane (CPA), and 1,2-dichloroethane (DCA) were used as model compounds.

The direct reaction between substrates and ozone predominated at lower pH, which resulted in the efficient oxidation of the olefin, DCPE. At higher pH, ozonation resulted in more efficient oxidation of the chlorinated alkanes, with a corresponding decrease in the efficiency of DCPE oxidation. Consistent results were observed for ozone/H₂O₂ and ozone/UV treatment. Due to slow UV-induced decomposition of H₂O₂, the process using H₂O₂/UV (254 nm) resulted in very slow oxidation of all four compounds.

The total ozone requirement to achieve a given degree of elimination (to 37% of the original concentration), δ0.37, was used to assess the combined effects of the direct and indirect reactions for different types of waters.     

SBA-15锚定的钌杂多酸催化剂的合成及其催化正十六烷氧化

利用(3-氨丙基)三乙氧基硅烷(apts)将钌金属杂多酸[X₂W₂₀O₇₀(RuY)₂]^10-(其中,X为锑或铋,Y为苯或对异丙基苯甲烷)固定在介孔的SBA-15上可得到一系列性能优良的SBA-15锚定的钌杂多酸催化剂。采用XRD、N₂吸附-脱附实验和FT-IR红外光谱对此类催化剂进行表征,并检测其对正十六烷氧化的催化性能。结果表明,以空气为氧化剂,在无任何溶剂的条件下,该锚定的钌杂多酸催化剂遵循传统的自由基自氧化机理,将正十六烷烃氧化成各种醇类和酮类,显示出优良的催化性能。因此,这类多相催化剂对环境友好的烷烃氧化反应具有较高的应用价值。     

Influence of additives on microstructure and property of microarc oxidized Mg–Si–O coatings

Ceramic coatings were fabricated on ZK60 magnesium alloy substrate by microarc oxidation (MAO) in Na₂SiO₃–KOH base electrolyte with four kinds of additives (i.e. KF, NH₄HF₂, C₃H₈O₃ and H₂O₂). The effects of these additives on microstructure and property of coatings were investigated. The surface morphology, phase composition and corrosion resistance of the ceramic coatings were analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and simulation body fluid (SBF) immersion test respectively. It is found that different additives can change the spark discharge phenomenon during microarc oxidation. It is proved that both potassium fluoride (KF) and ammonium bifluoride (NH₄HF₂) promote discharge and accelerate reaction while the introduce of glycerol (C₃H₈O₃) leads to the refining of sparks and reduction of thermal effects. Results also demonstrate that the introduce of hydrogen peroxide (H₂O₂) contributes to the increase of coating surface roughness and enlargement of surface micropore size. XRD results indicate that the ceramic coatings are mainly composed of Mg₂SiO₄, MgSiO₃ and SiO₂. The introduce of H₂O₂ hinders the reaction between SiO₂ and MgO and creates favorable conditions for the formation of the MgO phase. The ceramic coatings formed in base electrolyte containing 7 g/L NH₄HF₂ and 5 mL/L C₃H₈O₃ exhibit the highest corrosion resistance.