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.     

Oxidation of 1,3,5‐trichlorobenzene using advanced oxidation processes

The oxidation of 1,3,5‐trichlorobenzene (TCB) by ozone, ozone/UV, ozone/H₂O₂ and ozone/UV/H₂O₂ was studied. All studies were conducted in a continuously‐flowing completely mixed reactor (CFCMR), operated at steady‐state conditions using a hydraulic retention time of 10 minutes. The greatest removal of TCB using ozone/H₂O₂ treatment was achieved using a H₂O₂ concentration of 60 μM. At low pH values (approx. 2) ozone/UV performed significantly better than either ozone alone or ozone/H₂O₂. However, at circumneutral pH, the removal efficiencies of TCB by ozone/UV and ozone/H₂O₂ and ozone/UV/H₂O₂ were essentially equal (～ 97% for TCB). The removal efficiency of ozone alone was ～93% for TCB. At high pH (> 9) there was no advantage in supplementing ozone with either UV or H₂O₂ as the removal efficiencies for all processes studied were essentially equal.

The effect of humic acid and bicarbonate on the removal of TCB was studied. At 1.6 mg/L humic acid, 92–95% of the TCB was oxidized by the processes studied. The removal of TCB by ozone alone was significantly affected by the presence of bicarbonate ion. For the other processes at 10 mM bicarbonate, approximately 80% of the TCB was oxidized.     

Combination of Ozone with Activated Carbon as an Alternative to Conventional Advanced Oxidation Processes

The objective of this study was to compare the efficiency of O₃/granular activated carbon (GAC) to enhance ozone transformation into ·OH radicals, with the common advanced oxidation processes (O₃/OH^?, O₃/H₂O₂). The results obtained with model systems under the given experimental conditions showed that the system O₃/OH^? (pH 9) and O₃/H₂O₂ (pH 7, [H₂O₂] = 1·10^?5 M) are more efficient than O₃/GAC (pH 7, [GAC] = 0.5 g/L) to enhance ozone transformation into ·OH radicals. However, in Lake Zurich water the O₃/GAC process has a similar efficiency as O₃/H₂O₂ for ozone transformation into ·OH radicals. The results also show that the presence of GAC during Lake Zurich water ozonation leads to (i) removal of hydrophilic and hydrophobic micropollutants, (ii) reduction of the concentration of CO₃ ^2?/HCO₃ ^?, and (iii) decrease of the concentration of dissolved organic carbon (DOC) present in the system.     

Ceramic Raschig Rings—Improving Removal of Organic Compounds from Landfill Leachate by Perozone (O3/H2O2)

For improving the treatment of landfill leachate by combination O₃/H₂O₂, ceramic Raschig rings (CRR) with different surface areas were added to enhance mass transfer of ozone into liquid phase. To determine optimal conditions of reaction, pH and reaction time was also studied. The optimal pH range of 8–9, optimal reaction time of 80 min was identified in this research. CRR contribute to the significant improvement of efficiency of landfill leachate treatment by O₃/H₂O₂ systems. With added CRR of 728 m²/m³ surface area, color, COD and TOC removal was increased in comparison with experiment without CRR is 8%, 14%, and 9%, respectively. In this condition, the ozone utilization efficiency was also higher than that of experiment without CRR. Content of O₃ was also identified uses 3.441 kg O₃/kg COD.     

Evaluation of O3/UV and O3/H2O2 as Practical Advanced Oxidation Processes for Degradation of 1,4-Dioxane

The degradation of 1,4-dioxane was investigated on a laboratory scale. The extents of degradation and/or removal of 1,4-dioxane by ozonation at pH 6–8, UV irradiation, aeration, and addition of H₂O₂ were very limited. On the other hand, the degradation of 1,4-dioxane by O₃/UV and O₃/H₂O₂ was accelerated compared with the above respective methods. The amounts of 1,4-dioxane degraded per amount of ozone consumed in O₃/UV and O₃/H₂O₂ were also higher than in ozonation. The amount of 1,4-dioxane degraded in O₃/UV was affected by the intensity of UV irradiation, and that in O₃/H₂O₂ was affected by the amount of H₂O₂ added only in the case of a high initial concentration of 1,4-dioxane.     

Reaction of Ozone with Ag(I)—Mechanistic Considerations

Ozone reacts slowly with Ag⁺ (circumneutral pH, k = (11 ± 3) × 10^?2 M^?1 s^?1). After some time, ozone decay kinetics may suddenly become faster with the concomitant formation of silver sol. As primary process, an O-transfer from O₃ to Ag(I) is suggested, whereby Ag(III) is formed [Ag⁺ + O₃ + 2 H₂O → Ag(OH)₃ + O₂ + H⁺]. This conproportionates with Ag(I), which is in large excess, leading to Ag(II) [Ag⁺ + Ag(OH)₃ ? 2 Ag(OH)⁺ + HO^?]. Further, Ag(II) reacts with ozone in a high exergonic reaction [Ag(OH)⁺ + O₃ → Ag + 2 O₂ + H⁺], where ozone acts as a reducing agent. Thereby, a single silver atom, Ag, is formed that can be oxidized by O₂ and O₃ or can aggregate to a silver sol. Aggregation slows down the rate of oxidation. When Ag⁺ is complexed by acetate ions, ozone decay and silver sol formation are speeded up by enhancing Ag(II) formation [Ag(I)acetate + O₃ → Ag(III)acetate → Ag(II) + CO₂ + ?CH₃]. In the presence of oxalate, the formed complex reacts faster with ozone than Ag⁺, and Ag(III)oxalate decarboxylates rapidly [Ag(I)oxalate + O₃ → Ag(III)oxalate → Ag⁺ + 2 CO₂]. This enhances ozone decay but prevents silver sol formation. Quantum chemical calculations have been carried out for substantiating mechanistic suggestions.     

Determination of Rate Constants for Ozonation of Ofloxacin in Aqueous Solution

The ozonation of the quinolone antibiotic ofloxacin in water has been investigated with focus on kinetic parameters determination. The apparent stoichiometric factor and the second-order rate constants of the reactions of ozone and hydroxyl radical with ofloxacin were determined at 20 °C in the pH range of 4–9. The apparent stoichiometric factor was found to be about 2.5 mol O₃/mol ofloxacin regardless of the pH. The rate constant of the reaction between ozone and ofloxacin was determined by a competitive method (pH = 6–9) and a direct ozonation method (pH = 4). It was found that this rate constant increases with pH due to the dissociation of ofloxacin in water. The direct rate constants of ofloxacin species were determined to be 1.0?×?10², 4.3?×?10⁴ and 3.7?×?10⁷ for cationic, neutral-zwitterion and anionic species, respectively. Accordingly, the attack of ozone to ofloxacin mainly takes place at the tertiary amine group of the piperazine ring, though some reactivity is also due to the quinolone structure and oxazine substituent. The rate constant of the reaction between ofloxacin and hydroxyl radical was obtained from UV/H₂O₂ photodegradation experiments. It was found that this rate constant varies with pH from 3.2?×?10⁹ at pH 4 to 5.1?×?10⁹ at pH 9.     

Effect of UV Radiation on the Removal of Carboxylic Acids from Water by H2O2 and O3 in the Presence of Metallic Ions

The effect of UV radiation on the removal of formic, oxalic and maleic acids from water by metallic ion (Fe²⁺ or Cu²⁺)/H₂O₂ and metallic ion/O₃ was studied and compared. The results showed that metallic ion/O₃/UV has higher efficiency than metallic ion/H₂O₂/UV for oxalic acid removal. UV radiation significantly increases the efficiency of metallic ion/H₂O₂ for formic and maleic acids removal while its effect on the efficiency of metallic ion/O₃ for formic acid removal is minor_. However, at pH 2, O₃ alone showed higher efficiency than metallic ion/H₂O₂/UV for formic acid removal. Contrary to the relative efficiency of metallic ions in the previous systems, Cu²⁺ exhibited higher rate than Fe²⁺ for the removal of the degradation products of maleic acid by O₃. UV radiation exhibited a minor effect on the efficiency of Cu²⁺/O₃, while it exhibited a large effect on the efficiency of Fe²⁺/O₃ for the removal of the degradation products of maleic acid.     

ELIMINATION OF BENZENE AND CHLOROBENZENES BY PHOTODEGRADATION AND OZONATION PROCESSES

Benzene (B) and two representative chlorobenzenes (1,4-dichlorobenzene (DCB) and 1,2,3-trichlorobenzene (TCB)) were oxidized by means of UV irradiation alone, ozone alone, and the combinations UV/H₂O₂ and O₃/H₂O₂. In the single photolytic process, the influence on the photodegradation of the pH, temperature, and type of radiation source used was established. A kinetic study was performed by evaluating the first-order rate constants and the quantum yields. The effect of the additional presence of hydrogen peroxide was pointed out in the combined process UV/H₂O₂,with the determination of the specific contribution of the radical pathway to the overall photodegradation system. In the oxidation by ozone based systems (ozone alone and the combination O₃/H₂O₂), the rate constants at 20°C for the reaction of each compound with ozone and hydroxyl radicals were determined.     

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.     

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.     

Kinetic Study of Ozone Decay in Homogeneous Phosphate-Buffered Medium

The ozone decomposition reaction is analyzed in a homogeneous reactor through in-situ measurement of the ozone depletion. The experiments were carried out at pHs between 1 to 11 in H₂PO₄^?/HPO₄^2– buffers at constant ionic strength (0.1 M) and between 5 and 35 °C. A kinetic model for ozone decomposition is proposed considering the existence of two chemical subsystems, one accounting for direct ozone decomposition leading to hydrogen peroxide and the second one accounting for the reaction between the hydrogen peroxide with the ozone to give different radical species. The model explains the apparent reaction order respect of the ozone for the entire pH interval. The decomposition kinetics at pH 4.5, 6.1, and 9.0 is analyzed at different ionic strength and the results suggest that the phosphate ions do not act as a hydroxyl radical scavenger in the ozone decomposition mechanism.     

Oxidation of Aqueous Dimethyl Sulfoxide (DMSO) Using UV,O3, and UV/O3

Dimethyl sulfoxide (DMSO) is extensively used in industry and a large amount of wastewater that contains DMSO is discharged. This investigation evaluates the feasibility and effectiveness of the use of UV, O₃ and UV/O₃ to degrade aqueous DMSO. DMSO oxidation tests were performed with initial DMSO concentrations of 400–890 mg/L, at various ozone dosages (5.44, 8.25, 12.80 mg/L.min), solution pH values (acidic, alkaline, uncontrolled), and UV irradiation power intensities (0 and 2.25 W/L). Experimental results demonstrated that acidic conditions favored the degradation of DMSO and increased the mass of DMSO decomposition per unit mass of ozone consumption, in both the presence and the absence of UV. DMSO exhibited zero-order degradation kinetics when sufficient ozone was supplied. The cost of the ozone or UV/ozone process per unit volume of wastewater with a DMSO concentration of 2500 mg/L is comparable to that of the UV/H₂O₂-biological and electrolysis-biological processes described in the literature.     

Oxidation of Esculetin,a Model Pollutant Present in Cork Processing Wastewaters,by Chemical Methods

The ozonation of esculetin (6,7-dihydroxycoumarin), a major pollutant present in the wastewater generated in the cork industry, was accelerated at high pH, with apparent second-order rate constants in the range from 3.3 × 10⁴ L/(mol·s) at pH=2 to 8.4 × 10⁷ L/(mol·s) at pH=9. The acid-base equilibrium of esculetin was studied, resulting in a pK_a value of 7.37. Taking into account this pK_a, the rate constants for the reaction between ozone and the un dissociated and dissociated forms of esculetin were 3.0 × 10⁴ and L/(mol·s) 6.67 × 10⁸ L/(mol·s), respectively. Apparent first-order rate constants for the photolysis by UV irradiation were also evaluated, with values between 0.12 × 10^?2 min^?1 at pH=2 and 1.15 × 10^?2 min^?1 at pH=9, while the quantum yields for this photo-degradation reaction varied from 0.99 × 10^?2 mol/Eins to 11.1 × 10^?2 mol/Eins at these pHs. The Fenton's reagent system was used for the generation of hydroxyl radicals, and the rate constant for the reaction between esculetin and these radicals was determined to be 1.06 × 10¹⁰ L/(mol·s). Finally, several chemical oxidation systems were used in the degradation of this pollutant: single oxidants (ozone, UV irradiation) and advanced oxidation processes (Fenton's reagent, UV/H₂O₂, O₃/H₂O₂, O₃/UV, O₃/H₂O₂ /UV, and photo-Fenton system). The results revealed that the most efficient methods in terms of esculetin removal were ozonation among the single oxidants, and the photo-Fenton system among the combined processes.     

Degradation of Polyvinylpyrrolidone by Photocatalytic Ozonation and Evaluation of the Influence of Some Operational Parameters

Photocatalytic degradation of polyvinylpyrrolidone (PVP) by titanium dioxide and ozone in an annular reactor was investigated using a 125-W mercury vapor lamp as the light source. It was observed that the TiO₂/O₃/UV process presented a greater efficiency than the TiO₂/UV process. In fact, around 90% of the mineralization was obtained in 1 h of reaction, reflecting the synergistic effect of the combination of O₃ and TiO₂ under UV light, because the sum of the rate constants of the individual processes is less than the rate constant of the combined process. The effects of the initial PVP concentration, photocatalyst dosage, ozone input flow rate and pH on the PVP degradation rate were studied. In general, the results suggest that PVP can undergo a cross-linking process when the TiO₂/O₃/UV treatment is applied. The reaction rate was increased when the photocatalyst dosage was increased up to 2.0 g L^?1; however, increasing the initial PVP concentration led to a drop in the reaction rate. The efficiency also decreased at basic pH, because ozone is decomposed under alkaline conditions. In addition, it was noted that most of the nitrogen atoms of the macromolecules of PVP can be transformed into nitrate and ammonia during photocatalytic ozonation.     

Ozonation of Exhausted Reactive Dye-Bath Analogues: the Use of Atrazine as an OH* Probe Compound

Ozonation and O₃/H₂O₂ treatment of a spent reactive dye–bath analogue containing aminofluorotriazine type reactive dyestuffs were examined in semi–batch experiments at different pH (2, 7 and 12), bicarbonate (0.18 M at pH7) and carbonate (0.19 M at pHl2) alkalinity. Atrazine (23.2 µM) was added as an OH* – sensitive probe compound to the reactive dye–bath analogue to evaluate the individual contributions of both direct molecular (O₃) and indirect radical (OH*) type reaction pathways for the treatment of spent dye–bath ingredients. From the obtained results it was evident that particularly de–aromatization (expressed in terms of UV₂₅₄ and UV₂₇₀ removal) kinetics were significantly retarded in the presence of HCO₃, CO₃ ^2‐ and particularly H₂O₂. O₃ decomposition and consumption increased appreciably when H₂O₂ (0.125 mM at pH7) was added as compared in the presence of carbonate/bicarbonate alkalinity when H₂O₂ was added indicating that H₂O₂ and alkalinity could act as radical chain reaction promoters (carriers) and inhibitors, respectively. Atrazine degradation and UV₂₇₀ abatement rates paralleled each other revealing that particularly de–aromatization of the spent dye–bath constituents mainly involves the action of OH*. Nitrate formation was distinctly higher at pH7 than at pH 12 as a consequence of the stronger OH* scavenging effect of carbonate alkalinity at pH12.     

O3/H2O2 Treatment of Methyl-terf-Butyl Ether in Contaminated Waters: Effect of Background COD on the O3-Dose

The destruction of methyl-tert-butyl ether (MTBE) in contaminated waters by O₃/H₂0₂ process was studied and the influence background COD, alkalinity, and hydrogen peroxide and MTBE concentrations on process treatment efficiency and ozone dosage was investigated. The treatment efficiency was evaluated by an Efficiency Index, which is based on electrical energy requirement for ozone production. It was found that the treatment efficiency decreases linearly with increasing concentrations of MTBE at constant background COD and with background COD at constant MTBE concentration. A simplified kinetic scheme was presented to account for these observations.     

Advanced oxidation processes for destruction of cyanide from thermoelectric power station waste waters

Several advanced oxidation processes for the destruction of cyanide contained in waste waters from thermoelectric power stations of combined‐cycle were studied. Thus, oxidation processes involving ozonation at basic pH, ozone/hydrogen peroxide, ozone/ultraviolet radiation and ozone/hydrogen peroxide/ultraviolet radiation have been carried out in a semi‐batch reactor. All these methods showed that total cyanide can be successfully degraded but with different reaction rates, and the decrease in the total cyanide concentration can be described by pseudo‐first order kinetics. The influence of pH and initial concentration of hydrogen peroxide was studied to find the optimal conditions of the oxidation process. Experimental results of the single ozone treatment indicated that total cyanide is destroyed more rapidly at higher pH (12), while ozonation combined with H₂O₂ and/or UV is faster at pH 9.5. The optimum concentration of H₂O₂ was 20.58 × 10^?2 M because an excess of peroxide decreases the reaction rate, acting as a radical scavenger. The total cyanide degradation rate in the O₃/H₂O₂(20.58 × 10^?2 M ) treatment was the highest among all the combinations studied. However, COD reduction, in the processes using UV radiation such as O₃/UV or O₃/H₂O₂/UV was about 75%, while in the processes with H₂O₂ and/or O₃/H₂O₂ was lower than 57% and was insignificant, when using ozone alone. Copyright © 2003 Society of Chemical Industry     

Ozone-Based Advanced Oxidation Processes for the Decomposition of N-Methyl-2-Pyrolidone in Aqueous Medium

The present study investigates the decomposition of N-Methyl-2-Pyrolidone (NMP) using conventional ozonation (O₃), ozonation in the presence of UV light (UV/O₃), hydrogen peroxide (O₃/H₂O₂), and UV/H₂O₂ processes under various experimental conditions. The influence of solution pH, ozone gas flow dosage, and H₂O₂ dosage on the degradation of NMP was studied. All ozone-based advanced oxidation processes (AOPs) were efficient in alkaline medium, whereas the UV/H₂O₂ process was efficient in acidic medium. Increasing ozone gas flow dosage would accelerate the degradation of NMP up to certain level beyond which no positive effect was observed in ozonation as well as UV light enhanced ozonation processes. Hydrogen peroxide dosage strongly influenced the degradation of NMP and a hydrogen peroxide dosage of 0.75 g/L and 0.5 g/L was found to be the optimum dosage in UV/H₂O₂ and O₃/H₂O₂ processes, respectively. The UV/O₃ process was most efficient in TOC removal. Overall it can be concluded that ozonation and ozone-based AOPs are promising processes for an efficient removal of NMP in wastewater.     

Decomposition of Detergents in Industrial Wastewater by AOP in Flow Systems

The present studies covered investigations of advanced oxidation of detergents in industrial wastewater with the use of ozone, hydrogen peroxide, UV and ionizing radiation separately and in combinations: O₃+UV, UV+H₂O₂, H₂O₂+O₃, O₃+H₂O₂+UV, O₃+ ionizing radiation in the flow systems taking into account specific features of subsequent versions. The aim of these studies was to present results of detergent decomposition in the applied versions and also in the flow systems compared to stationary systems. The radiation processes were carried out with high efficiency in all stationary and flow systems tested. The best results of detergent decomposition were achieved in the samples exposed to simultaneous radiation and ozonation.