Estimation Of The Relative Importance Of Free Radical Oxidation And Direct Ozonation/UV Radiation Rates Of Micropollutants In Water

The relative importance of free radical and direct ozonation/photolysis oxidation of micropollutants in water can be estimated from simple kinetics of aqueous ozonation reactions provided these reactions develop in the slow kinetic regime of absorption. Knowledge of kinetic expressions of free radical initiation reactions and direct ozone-micropollutant or UV radiation-micropollutant reactions (and corresponding parameters: reaction rate constants, quantum yields, etc.) allows an estimation of the reaction rate ratios for any micropollutant in the ozone alone and combined with hydrogen peroxide and/or UV radiation oxidation systems.     

Ozonation Kinetics Of Glucosamine And N-Acetyl Glucosamine In Aqueous Medium

Glucosamine and N-acetyl glucosamine show different behaviors towards ozone in aqueous medium: while glucosamine reacts relatively fast through ozone attack on the amino group, N-acetyl glucosamine is much more resistant, resembling the reactivity of glucose. Results obtained indicate that a mechanism of viral inactivation via ozone attack on the N-acetyl glucosamine of the viral capsid is not kinetically favored.     

Advanced Oxidation Processes Against Phenolic Compounds In Wastewater Treatment

Experimental research into the oxidative treatment of aqueous solutions and wastewaters containing phenolic compounds was undertaken. Ozone, supported by short wavelength UV-irradiation, hydrogen peroxide and titanium dioxide catalyst, was selected as an oxidant in the following combinations: O₃, O₃/H₂O₂, O₃/UV, O₃/TiO₂, O₃/UV/H₂O₂ and O₃/UV/TiO₂. 5-Methylresorcinol was chosen as a model compound for the experiments with synthetic phenolic solutions. The results obtained from these experiments were compared with the results of oxidative purification of wastewaters produced from the thermal treatment of oil shale in Estonia.     

Ultraviolet-Enhanced Ozonation of Organic Compounds: 1,2-Dichloroethane and Trichloroethylene as Model Substrates

1,2–Dichloroethane (DCE) and trichloroethylene (TCE) were used as model compounds to study the oxidation of organic chemicals by ozone/ultraviolet radiation, ozone, and hydrogen peroxide/ultraviolet radiation. It was found that ozone/ultraviolet radiation oxidized both 1,2–dichloroethane and trichloroethylene in batch systems, at pH = 2 (phosphate buffer). At ozone concentrations in the 1 to 5 mg/L range, the reaction was first order in both ozone and substrate. At pH = 2 and initial ozone concentration 2.2–2.6 mg/L, rate constants (k)Q = 25 and 130 M^-1sec^-1 were observed for the ozone/ultraviolet radiation oxidation of DCE and TCE, respectively. The rat e constants for ozone oxidation of DCE and TCE without ultraviolet radiation were 4.3 and 47 M^-1sec^-1, respectively.

The higher rate of TCE oxidation implies that direct reaction occurs with the double bond. Finite reaction rate of DCE with ozone, and substantial increases in rate at higher pH imply the participatation of hydroxyl radicals in the oxidation of both compounds. For example, at pH = 7, initial ozone concentration of 2.3 mg/L, the k_o for TCE oxidation by ozone/ultraviolet radiation is approximately 500 M^?1 sec^?1 almost too fast to measure in a batch system.The rate also is increased by increased ultraviolet radiation intensity, and by the presence of hydrogen peroxide, which acts as a catalyst.     

Ozonation Kinetics Of o-phenylphenol in Aqueous Solutions

This study investigated the oxidation and reaction kinetics of biocide o-phenylphenol (o-PP) during ozonation. The second-order rate constants for direct reaction of molecular ozone with o-PP were determined in homogenous system using classical and competition kinetics. Obtained values of the second-order rate at pH 2 are equal to (3.79 ± 0.23)?×?10² M^?1 s^?1 and (4.42 ± 0.64)?×?10² M^?1 s^?1, for the two methods, respectively. The rate constant for the dissociated form of o-PP was also determined. It was found that the rate constants for the reaction of o-PP with ozone increase significantly with increasing pH.     

Theoretical Aspects Of The Kinetics Of Competitive First Reactions Of Ozone In The O3/H2O2 And O3/UV Oxidation Processes

Kinetics of competition between the ozone direct reaction with compounds in water, ozone-hydroperoxide ion reaction leading to free radicals in the O₃/H₂O₂ process, and the photolysis of ozone in the O₃/UV process are discussed in terms of diffusion and reaction times to establish conditions for these reactions to be competitive. Film theory and chemical kinetic concepts then are applied to estimate initial rates of ozone absorption and consumption, removal rates of compounds present in water, and the importance of the radical oxidation path versus direct ozone and/or photolysis reactions.     

Vapor and Liquid Phase Ozonation of Benzene

A comparative study is made of the benzene-ozone reaction in the gaseous and aqueous phase reactors at atmospheric pressure and 25°C. The vapor phase ozonation of benzene is first order in ozone and independent of benzene concentration. In distilled water (pH ranging from 5.2 to 5.4), the reaction is one-half order with respect to both concentrations of dissolved benzene and ozone. The overall rate constants are 0.0011 and 2.67 s^?1, respectively, in the vapor and liquid phase reactions. Results of this study suggest that it is technically feasible to remove benzene from a gas stream by the ozonation process, although the reaction rate is slow.     

The Basic Principles of UV–Disinfection of Water

The disadvantage of chlorination of drinking water is the possible synthesis of toxic chlorinated fragments. In different cases UV can be an alternative to chlorination. The germicidal effectiveness of UV–radiation is in the 180–320 nm region with an optimum at 265 nm. Approximately 95% of the energy radiated by a low–pressure mercury arc is at the 253.7 nm line, so this source is the most effective one for germicidal applications. The germicidal effectiveness of a broadband source can be calculated. UV alone cannot decrease the concentrations of organic contaminants of the treated water. Quite promising are the systems where UV–radiation acts as a catalyst in oxidation reactions in order to decrease the organic contaminants.     

Ozonation Of Wastewater Resulting From The Production Of Organochlorine Plaguicides Derived From DDT And Trichlorobenzene

In this work, a first step has been made in the characterization of the organic pollutants found in the residual water from the production of dicofol and tetradifon pesticides, derived from DDT and trichlorobenzene, respectively. The behavior of the effluent also was studied using degradation techniques - treatment with ozone and ozone combined with hydrogen peroxide - and the results compared by means of the pH, conductivity, TOC, COD, TOX, ecotoxicity, GC/ECD and GC/MS analysis of the samples after the treatment.     

Ozonation And AOP Parameter Estimation From Countercurrent Film Absorber Data

Degradation of phenolic compounds in Kohtla-Järve oil shale ash dump wastewater (North-East Estonia) by O₃, O₃/UV, O₃/H₂O₂, O₃/H₂O₂/UV, O₃/TiO₂ and O₃/TiO₂/UV treatment in a countercurrent film absorber was studied experimentally. The mathematical model and the simulation algorithm of the processes were developed. The random search optimizer was applied to evaluate the values of reaction rate constant, mass transfer enhancement factor, stoichiometric coefficient and volatilization coefficient for organics into the process models. The evaluated coefficients for individual phenolic compounds, total content of phenolic compounds and COD for different oxidation systems are presented and discussed. “Operation” of the simulated film absorber (based on the evaluated coefficients) and the experimental column are compared.     

Efficiency of Ozonation and AOP for Methyl-tert-Butylether (MTBE) Removal in Waterworks

Methyl-tert-butylether (MTBE) is attracting more and more attention since it was discovered in groundwater and other raw water sources for waterworks and proved to difficult to remove during conventional treatment steps in drinking water production. Therefore advanced treatment processes have to be evaluated in addition to established treatment technologies. Laboratory based experiments were carried out studying ozonation with varying ozone concentrations at different pH values. For the elimination of MTBE the degradation through hydroxyl radicals was identified as the main degradation pathway. No decline of MTBE concentration occurred in experiments with molecular ozone, but AOP (Advanced Oxidation Processes) experiments where hydrogen peroxide (H₂O₂) was added showed a more efficient elimination. However, no complete mineralization was achieved — tert-butyl alcohol (tBA) and tert-butyl formate (tBF) were identified as metabolites. In natural waters (i.e., groundwater, bank filtrated water, and drinking water) the efficiency of MTBE removal was strongly dependent on the content of natural organic matter and alkalinity because of their scavenging characteristics. However, bromate formation was observed as well and could cause problems for drinking water production. Comparison with data gained from waterworks showed that conventional ozonation techniques as applied in waterworks are not able to remove MTBE efficiently.     

Ozonation Kinetics of Six Dichlorophenol Isomers

This paper investigates the kinetics of reactions between dichlorophenol (DCP) isomers and dissolved ozone in solutions of pH varying from 2 to 6 at 5 to 35 °C. A DCP can exist as dichlorophenol molecules and dichlorophenoxide anions in the aqueous solution, and both forms are reactive toward ozone. The overall reaction is second order requiring two moles of ozone for conversion of each mole of DCP. The ozonation rate of 2,6-DCP is the fastest and that of 3,4-DCP is the slowest at an identical condition. The Arrhenius equation is applicable to correlate temperature effects; the activation energy ranges from 46.5 to 55.3 kJ/mol. The reaction rate increases very rapidly as the acidity decreases, and the overall rate constant is greater than 1x106 M-1s-1 in solutions with pH of 5 or larger at 25 °C. The results of this study suggest that DCPs can be removed rapidly from wastewaters by ozone treatment.     

Henry And Mass Transfer Coefficients In The Ozonation Of Wastewaters

A procedure for the determination of Henry and mass transfer coefficients in an ozone-industrial wastewater system is presented. The method is applied to the ozonation of a tomato plant industrial wastewater, developed in the slow kinetic regime. In so doing, molar balances of ozone (in gas and water phases) are used together with gas-liquid reaction kinetic theory. While Henry's coefficients obtained are similar to those corresponding to ozonation in organic-free water, significant deviations are observed regarding the mass transfer coefficient.     

Ozone,Hydrogen Peroxide/Ozone And UV/Ozone Treatment Of Chromium- And Copper-Complex Dyes: Decolorization And Metal Release

Metal-complex azo dyes constitute a significant fraction of the dyes used in the textile industry and exhibit properties such as superior light- and wash-fastness. While effluent color is not always regulated, the textile finishing industry often decolorizes wastewater using processes including chemical oxidation. In this study, the use of ozone, hydrogen peroxide/ozone and UV/ozone oxidant systems was examined for treatment of two common metal-complex (premetalized) dyes, Acid Black 52 (chromium) and Direct Blue 80 (copper). Oxidant dosages required for decolorization of these dyes were determined. The effect of bicarbonate alkalinity on the ozonation and the hydrogen peroxide/ozone processes also was examined.     

Multistage Decomposition Kinetics of Ozone In Dilute Aqueous Solutions

AbstractDecomposition of ozone in dilute aqueous solutions was found to be a complex process kinetically. Initial ozone dose-time had a significant impact on reaction order. Solutions dosed initially for less than one minute displayed uniform second-order kinetics. For doses applied over 5 and 15 min periods at a pH -2, reaction order changed from 2 to 1 to 0 as ozone decomposition progressed. At a pH of 6.65, the transition was from a reaction order of 2.5-3 to 2. This behavior has been ascribed to the effect of accumulated ozone decomposition products on the decomposition process.     

Effects Of Catalysts During Ozonation Of Salicylic Acid,Peptides And Humic Substances In Aqueous Solution

The oxidation of two model molecules (salicylic acid and a peptide) and humic substances in aqueous solution was studied using ozone in the presence of various catalysts. Experiments were performed in reactors operated either in batch (TOC_o = 2.5 mg C.L^?1) or in semi-continuous flow mode (TOC_o = 42 mg C.L^?1).     

Improvement in the Effectiveness of Ozonation of Drinking Water Through the Use of Hydrogen Peroxide

Addition of hydrogen peroxide to water during ozonation increases the rate of oxidation of organic compounds and ozone transfer. Coupling ozone with hydrogen peroxide can increase the efficiency of a drinking water treatment line, for example in removing THM precursors. To optimize this oxidation process, the quantity of hydrogen peroxide added and the point of injection must be carefully selected.     

Ozonation,Ozone/UV and UV/H2O2 Degradation of Chlorophenols

The performance of the O₃, O₃/UV and UV/H₂O₂ processes for degradation of six chlorophenols (4-chlorophenol, 2-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol and pentachlorophenol) were studied in laboratory reactors. Comparative study showed that chlorophenols can be degraded successfully by all of the methods studied, whilst traditional ozonation at high pH was determined to be the most effective method to treat chlorophenols. Even though the molar absorptivity of chlorophenols is known to be relatively high in the UV-region, the combination of UV-radiation with ozone did not accelerate the degradation of chlorophenols further. The toxicity of degradation products formed during ozonation of chlorophenols has been compared with the toxicity of pure chlorophenols utilizing Daphnia magna 24 hours test. Ozonation of chlorophenols yielded less toxic or even nontoxic products for Daphnia magna compared with parent compounds.     

Efficiency Of Ozonation As A Unit Process In The Treatment Of Secondary Effluents From the Pulp And Paper Industry

Experiments were run in a batch reactor on samples of wastewater from pulping processes and paper making after biological treatment (secondary effluent). The samples then were treated in the following technological systems: ozonation alone, ozonation with alum or lime coagulation as a prior step, and ozonation with chlorination as a prior step. Of these, the coagulation-ozonation system was found to be the most effective, yielding high removal efficiencies.     

The Combination of Ozone/Hydrogen Peroxide and Ozone/UV Radiation for Reduction of Trihalomethane Formation Potential in Surface Water

Applied ozone dosages of 20, 25, and 30 mg/L to lake water utilized by the city of Shreveport, LA produced no significant reductions in trihalomethane formation potentials (THMFP). However, the addition of 20 mg/L of hydrogen peroxide and/or 0.67 W/L of UV radiation (254 nm) in combination with ozone produced decreases in THMFP of over 60% in 60 minutes. Smaller THMFP decreases were seen with shorter contact times. The use of H₂O₂ and/or UV in combination with O₃ increased the percentage of applied ozone consumed by the lake water (i.e., enhanced the ozone mass transfer) five times over simple ozonation.