Direct Ozone Reaction Research Articles

Sequential Process of Electro-Oxidation Followed by UV Photolysis (EO/UV) as a Simple Advanced Oxidation Process

ABSTRACT A sequential process of electro-oxidation followed by UV photolysis (EO/UV) was proposed as a simple advanced oxidation process. A boron-doped diamond (BDD) anode was used for electrolysis. A series of experiments revealed that the EO/UV significantly enhanced 1,4-dioxane degradation rate against single electro-oxidation and single UV photolysis. In the EO/UV of tap water, reactive radicals produced through UV photolysis of electrochemically generated ozone and free chlorine contributed to 28–53% of 1,4-dioxane degradation and the rest of the contribution was occupied by anodic oxidation. Indirect and direct ozone reactions did not take part in the 1,4-dioxane degradation. The energy efficiency of EO/UV was superior to that of single electro-oxidation at a higher current density and was stable in the electrolytic current range tested. Consequently, EO/UV was more effective in the rapid removal of 1,4-dioxane under an unsteady pollutant loading than the single electro-oxidation.

On the importance of reactions in the proximity of the gas–water interface: Application to direct ozone reactions of antibiotics in water

A comparison between kinetic models of the direct ozonation in water of a mixture of fifteen antibiotics has been carried out by considering both the reactions in the proximity of gas–water interface (film reactions) and in the water bulk. Stoichiometric coefficients and rate constants of the O3-antibiotic reaction were determined following standard procedures and compared to the values reported in the literature. The importance of stoichiometric coefficients in the establishment of the ozone kinetic regimes and kinetic modelling has been discussed. Most of the antibiotics studied react under fast or moderate regime with ozone at the conditions applied. The significance of these reactions in the proximity of gas–water interface is discussed sustained in the application of film theory. Results have been compared to those obtained from the kinetic approach where ozone reactions in the film are not taken into account. The importance of reactions in the film represents >60% of antibiotics consumption. Deviations between experimental and simulated concentrations of antibiotics are due to the contribution of reaction intermediates to ozone consumption, which is not considered in the kinetic model.

Study on the Mechanism and Control Strategy of Advanced Treatment of Yeast Wastewater by Ozone Catalytic Oxidation

In this paper, the yeast wastewater secondary treatment effluent using catalytic odor oxidation treatment, using an orthogonal reaction experiment to determine the best reaction conditions, and the online monitoring of the pH, oxidation-reduction potential (ORP), and liquid ozone concentration monitoring, to the catalytic odor oxidation reaction, chemical oxygen demand (COD), and color removal effect were analyzed. The results showed that the optimal reaction condition for the advanced treatment of yeast wastewater by catalytic ozonation was accomplished with manganese dioxide used as the catalyst and a catalyst dose of 6 g·L−1, pH of 12, and catalytic ozonation reaction time of 20 min. The COD was effectively reduced from 880 mg·L−1 to 387 mg·L−1 under this condition, the chroma was reduced from 700 times to 40 times, and these two parameters of the effluent could meet the standard of GB25462-2010. The real-time monitoring system showed that the whole reaction can be divided into two processes. The first 14 min was the indirect reaction of ozone and then the direct oxidation reaction of ozone. This process was further verified by the change trend of COD and the amount of ozone depletion by COD removal. The average ozone consumption levels of the two stages were 1.97 and 4.91 mgO3·mgCOD−1. This system can effectively monitor the reaction of the catalytic odor oxidation in the complex system to guide the effective use of ozone in practical engineering applications.

Elimination of neonicotinoids by ozone-based advanced oxidation processes: Kinetics and performance in real water matrices

The Decision 2018/840 included some neonicotinoid insecticides (thiamethoxam (TMX), imidacloprid (ICP), clothianidin (CTD), thiacloprid (TCP), and acetamiprid (AMP)) within the watch list of substances for Union-wide monitoring in the field of water policy due to their potential risk to human health and the environment. In this work, the study of the elimination of these five neonicotinoids present in waters by ozone-based oxidation treatments has been carried out. While AMP and TCP presented very low rate constants with ozone and were hardly degraded, CTD (ozone rate constant of 116 M−1 s−1 at pH ≥ 7) and TMX (ozone rate constant of 22.7 M−1 s−1 for the studied pH range) were partially degraded by ozone. Furthermore, ICP ozonation showed a great pH dependence, with increasing ozone rate constant values from 2.7 M−1 s−1 at pH 5 to 160 M−1 s−1 at pH 9. In addition, rate constants for the reaction of neonicotinoids with hydroxyl radicals (•OH) were determined to be in the range (2.0–4.5)·109 M−1 s−1. The specific contribution of direct ozonation and radical pathways to the overall neonicotinoid degradation was evaluated, being the indirect oxidation with •OH dominant over direct ozone reactions. The influence of real water constituents such as dissolved organic matter (DOM) and bicarbonate, both acting as radical scavengers, on the ozonation process was negative. The ozone dose and the specific ozone dose required to remove neonicotinoids from real water matrices were higher than 5 mg/L and 1 mg O3 mg DOC-1, respectively, typically applied in water treatment. However, the application of the ozone-based advanced oxidation processes O3/H2O2 and O3/activated carbon provided an appreciable improvement in the elimination of neonicotinoids compared to ozone alone. Therefore, ozone-based advanced oxidation processes are needed to sufficiently abate neonicotinoids in contaminated waters.

Modeling the Mineralization Kinetics of Visible Led Graphene Oxide/Titania Photocatalytic Ozonation of an Urban Wastewater Containing Pharmaceutical Compounds

In a water ozonation process, dissolved organics undergo two reactions at least: direct ozone attack and oxidation with hydroxyl radicals generated from the ozone decomposition. In the particular case of urban wastewater contaminated with pharmaceuticals, competition between these two reactions can be studied through application of gas–liquid reaction kinetics. However, there is a lack in literature about kinetic modeling of ozone processes in water specially in photocatalytic ozonation. In this work, lumped reactions of ozone and hydroxyl radicals with total organic carbon have been proposed. Urban wastewater containing a mixture of eight pharmaceutical compounds has been used to establish the kinetic model that simulates the mineralization process. The kinetic model is based on a mechanism of free radical and molecular reactions and the knowledge of mass transfer, chemical reaction rate constants, and radiation transfer data. According to the model, both single ozonation and photocatalytic ozonation present two distinct reaction periods characterized by the absence and presence of dissolved ozone. In the first period (less than 10 min), pharmaceuticals mainly disappear by direct ozone reactions and TOC variation due to these compounds has been modeled according to gas–liquid reaction kinetics through a lumped ozone-pharmaceutical TOC fast second order reaction. The corresponding rate constant of this reaction was found to change with time from 3 × 105 to 200 M−1 s−1 with Hatta values higher than 0.3. In the second period (nearly 5 h), competition between direct and hydroxyl radical reactions takes place and a kinetic model based on a direct and free radical reaction mechanism is proposed. Main influencing parameters to be known were: Direct ozone reaction rate constant, catalyst quantum yield, and hydroxyl radical scavengers. The first two take values of 0.5 M−1 s−1 and 5 × 10−4 mol·photon−1, respectively, while a fraction of TOC between 10% and 90% that changes with time was found to possess hydroxyl radical scavenger nature.

Removal of Organic Micropollutants from a Municipal Wastewater Secondary Effluent by UVA-LED Photocatalytic Ozonation

Numerous contaminants of emerging concern (CECs) have been found in different water bodies. Directive 2013/39/EU and Decision 2018/840/EU are consequently being implemented in the field of water policies. Twelve CECs (e.g., isoproturon, ciprofloxacin, and clarithromycin are among those listed) were detected in a municipal wastewater secondary effluent by means of solid phase extraction and ultra-high-performance liquid chromatography with tandem mass spectrometry (SPE-UHPLC-MS/MS). Different advanced oxidation processes (AOPs), based on the combination of ozone, UVA-LED and powdered TiO2, were investigated for their removal in a semi-batch operation. In addition, TiO2-coated glass rings (P25R) were characterized with different techniques (SEM, WDXRF) and used for continuous mode operation in a packed bed reactor (PBR). Among the AOPs studied, ozone-based processes were found to be more efficient than heterogeneous photocatalysis. A kinetic study was performed showing that direct ozonation is the main oxidation pathway for CEC removal. Ozone was successfully decomposed in combination with UVA-LED and P25R, resulting in an apparent rate constant of 3.2 × 10−2 s−1 higher than in the O3/LED system (1.0 × 10−3 s−1) or with ozone alone (8.6 × 10−5 s−1). Hydroxyl radical reaction could prevail over direct ozone reaction for the most refractory compounds (e.g., isoproturon).

Free Radical and Direct Ozone Reaction Competition to Remove Priority and Pharmaceutical Water Contaminants with Single and Hydrogen Peroxide Ozonation Systems

ABSTRACTFrom the application of concepts derived from the gas-liquid absorption film model, the competition between ozone reactions with 72 water emerging or priority contaminants (pharmaceuticals, pesticides, polynuclear aromatic hydrocarbons, etc.) and the initiation steps of the hydroxyl radical decomposition of ozone in ozone alone and combined with hydrogen peroxide oxidation systems has been studied. With this information, the ozone preferential reaction, that is, the ozone direct reaction or the formation of free radicals and the kinetic absorption regime are known. In a second step, the ratio of removal rates of the contaminants studied by reacting with hydroxyl radical and ozone has also been estimated. With this, the way contaminants are preferentially removed (from their reaction with ozone or from the reaction with free radicals) can also be known and, hence, whether or not an ozone advanced oxidation system is convenient to be applied. For instance, most of the contaminants studied in this work at concentrations lower than 50 μgL−1 and hydrogen peroxide at concentrations lower than 50 mgL−1 react with ozone under chemical control regime so that both direct and free radical reactions theoretically compete. However, under chemical control, typical concentration of scavengers present in wastewater or surface water would inhibit the free radical reactions and, at least theoretically, for many contaminants studied here, the direct ozone reaction is the principal removal way. When mass transfer controls the process rate only contaminants with a hydroxyl and ozone rate constant ratio ≥ 1.6x106 M-1s-1 would be preferentially removed through free radical way.

Exploring ozonation as treatment alternative for methiocarb and formed transformation products abatement

Despite the high toxicity and resistance to conventional water treatments exhibited by methiocarb (MC), there are no reports regarding the degradation of this priority pesticide by means of alternative purification technologies. In this work, the removal of MC by means of ozonation was studied for the first time, employing a multi-reactor methodology and neutral pH conditions. The second-order rate constants of MC reaction with molecular ozone (O3) and formed hydroxyl radicals (OH·) were determined to be 1.7·106 and 8.2·109 M−1 s−1, respectively. During degradation experiments, direct ozone reaction was observed to effectively remove MC, but not its formed intermediates, whereas OH· could oxidize all species. The major identified TPs were methiocarb sulfoxide (MCX), methiocarb sulfoxide phenol (MCXP) and methiocarb sulfone phenol (MCNP), all of them formed through MC oxidation by O3 or OH· in combination with hydrolysis. A toxicity assessment evidenced a strong dependence on MCX concentration, even at very low values. Despite the OH· capability to degrade MC and its main metabolites, the relative resistance of TPs towards ozone attack enlarged the oxidant dosage (2.5 mg O3/mg DOC) necessary to achieve a relatively low toxicity of the medium. Even though ozonation could be a suitable technique for MC removal from water compartments, strategies aimed to further promote the indirect contribution of hydroxyl radicals during this process should be explored.

Assessment of a Stirred-Cell Reactor Operated Semicontinuously for the Kinetic Study of Fast Direct Ozonation Reactions by Reactive Absorption

A jacketed stirred-cell reactor, operated semicontinuously, was used to assess the kinetics of fast ozonation reactions by reactive absorption. The method was applied to the direct ozone reaction with resorcinol. A high resorcinol concentration was used to reach a steady state and to neglect byproduct accumulation. Thus, the mass-transfer rate and, consecutively, the reaction rate were deduced from the ozone mass balance in the gas phase. The gas- and liquid-phase mass-transfer coefficients were previously measured directly through ozone absorption under appropriate conditions. The results emphasized the high sensitivity of the reaction rate constant to the ozone physicochemical properties, especially its solubility, which is controversial in the literature. Therefore, several correlations used to calculate the ozone solubility in water were considered to calculate the second-order reaction rate constant, which varied from 3.57–4.68 × 105 L mol–1 s–1 at 20 °C to 9.50–12.2 × 105 L mol–1 s–1 at 35 °C. The a...

Effects of effluent organic matter (EfOM) on the removal of emerging contaminants by ozonation

Removal of emerging contaminants in wastewater treatment is essential to ensure the ecological health of the receiving water bodies. Ozonation is a promising technology to achieve this purpose but important wastewater characteristics affecting the optimal removal efficiency need to be elucidated. Secondary effluents contain effluent organic matter (EfOM), which can react directly with ozone as well as react as the initiator, promoter and inhibitor in the hydroxyl radical (.OH) chain reactions resulting from ozone decomposition. These different reaction modes of EfOM, coupled with alkalinity and pH value, collectively determine the ozone and .OH exposures and the degradation of pharmaceutical compounds by ozonation. In this study, we determined the rate constants of EfOM collected from two municipal wastewater treatment plants in terms of direct ozone reaction, initiation, promotion and inhibition at various pH values (pH 6.0–7.5) and temperatures (10–30 °C). The rate constants of direct reaction and initiation generally increased with the increasing pH value while the rate constants of promotion and inhibition did not vary significantly. All rate constants increased with the increasing temperature. The removal of ibuprofen, acetylsulfamethoxazole and metoprolol in diluted secondary effluent by ozonation can be fairly-well modeled by using the determined rate constants of EfOM.

Removal of Benzothiazole from Contaminated Waters by Ozonation: The Role of Direct and Indirect Ozone Reactions

AbstractBenzothiazoles are emerging chemical pollutants mainly coming from leather, paper and rubber industries; due to their use as: herbicides, corrosion inhibitors, anti-freezers, and vulcanisation accelerators. This article presents experimental data on ozone treatment of benzothiazole contaminated waters. The effect of the initial concentration of benzothiazole, ozone dosage, temperature (10-30 °C), and pH (2-9), on ozonation removal rate were assessed at bench scale. Experimental results show that reaction between ozone and benzothiazole could be approximated to a second-order kinetic law. Kinetic parameters for direct and indirect ozone reactions are estimated and temperature dependence of rate parameters is evaluated. Moreover, an initial degradation pathway of benzothiazole ozonation is proposed.

Catalytic ozonation with γ-Al 2 O 3 to enhance the degradation of refractory organics in water

Nowadays, heterogeneous catalytic ozonation appears as a promising way to treat industrial wastewaters containing refractory pollutants, which resist to biological treatments. Several oxides and minerals have been used and their behavior is subject to controversy with particularly the role of Lewis acid sites and/or basic sites and the effect of salts. In this study, millimetric mesoporous γ-Al2O3 particles suitable for industrial processes were used for enhancing the ozonation efficiency of petrochemical effluents without pH adjustment. A phenol (2,4-dimethylphenol (2,4-DMP)) was first chosen as petrochemical refractory molecule to evaluate the influence of alumina in ozonation. Single ozonation and ozonation in presence of γ-Al2O3 led to the disappearance of 2,4-DMP in 25 min and a decrease in pH from 4.5 to 2.5. No adsorption of 2,4-DMP occurred on γ-Al2O3. Adding γ-Al2O3 in the process resulted in an increase of the 2,4–DMP oxidation level. Indeed, the total organic carbon (TOC) removal was 14% for a single ozonation and 46% for ozonation with γ-Al2O3. Similarly, chemical oxygen demand (COD) removal increases from 35 to 75%, respectively. Various oxidized by-products were produced during the degradation of 2,4-DMP, but after 5 h ozonation 90% of organic by-products were acetic acid > formic acid ≫ oxalic acid. Some of the carboxylic acids were adsorbed on γ-Al2O3. The use of radical scavengers (tert-butanol) highlighted the involvement of hydroxyl radicals during catalytic ozonation with γ-Al2O3 in contrary to single ozonation, which mainly involved direct ozone reaction. γ-Al2O3 is an amphoteric solid with Lewis acid AlOH(H+) sites and basicAl-OH sites. After ozonation the amount of basic sites decreased due to carboxylates adsorption, while the Lewis acid sites remained constant as evidenced by FTIR. Several ozonation runs with γ-Al2O3 reported a progressive decrease of its catalytic activity due to the cumulative sorption of carboxylates on the basic sites. After 80 h of ozonation, a calcination at 550 °C allowed to recover allAl-OH basic sites and the initial activity of γ-Al2O3. A synthetic petrochemical effluent containing various petrochemicals (phenol, acetic acid, naphtenic acid, pyrene, naphtalene) was then treated with γ-Al2O3 with and without NaCl. Sodium ions prevented carboxylates adsorption on γ-Al2O3 leading to a higher efficiency of γ-Al2O3 in presence of NaCl and allowed to decrease the toxicity of the petrochemical effluent.

Megasonic Enhanced Photoresist Strip with DiO<sub>3</sub>

Twenty years ago dissolved ozone in DIW (DiO3) found its way into the semiconductor industry as a cleaning agent. DiO3 provides an effective replacement for Piranha (H2SO4, H2O2) cleans. The fundamental chemistry of ozone based cleaning is due to direct and indirect reactions of ozone and oxygen radicals (the so-called radical pathway). Due to its high oxidation rate the radical pathway can accelerate the reaction. Megasonic energy can act as an initiator for the radical pathway. At the same time, due to the creation of turbulence inside the boundary layer, the available ozone close to the surface is increased. In the present study this chemical physical combination was tested for improvement of photoresist strip rate.

Catalytic ozonation for the removal of organic contaminants in water on ZSM-5 zeolites

The results presented in this study aim to show the potential of ozonation of common water pollutants (volatile organic chemicals, pharmaceuticals and carboxylic acids, ozonation by-products) on ZSM-5 zeolites and to investigate the effect of the nature of pollutants on the efficiency of catalytic ozonation. Both the H-ZSM-5 and Na-ZSM-5 forms with different SiO2/Al2O3 ratios and counter ions (Z1000H:SiO2/Al2O3=1000, Z900Na:SiO2/Al2O3=900, Z25H:SiO2/Al2O3=25 and Z25Na:SiO2/Al2O3=25) have been used. The effects of pH, adsorption, presence of hydroxyl radical scavengers, phosphates and humic acids on the efficiency of catalytic ozonation have been investigated. The results revealed that catalytic ozonation on zeolites could substantially enhance the removal of VOCs and ibuprofen when compared with ozonation alone and that adsorption plays a key role in the effectiveness of this process. Zeolites with high SiO2/Al2O3 ratios were found to have a high adsorption capacity towards VOCs and as a result high catalytic activity. On the other hand zeolites with low SiO2/Al2O3 ratios had a high adsorption capacity towards ibuprofen in its ionised form. Catalytic processes have been found to be pH dependent with the highest activity at acidic pH. The presence of hydroxyl radical scavengers (phosphates and humic acid) did not have a significant effect on the removal of contaminants on ZSM-5 zeolites. Despite high activity towards VOCs and ibuprofen, zeolites did not catalyse the removal of acetic acid in water at studied pH values. It is therefore suggested that catalytic ozonation of organic pollutants on ZSM-5 zeolites proceeds via direct reactions of molecular ozone with pollutants adsorbed on the surface of zeolites.

Decomposition of Lignin from Sugar Cane Bagasse during Ozonation Process Monitored by Optical and Mass Spectrometries

Mass spectrometry was used to monitor neutral chemical species from sugar cane bagasse that could volatilize during the bagasse ozonation process. Lignin fragments and some radicals liberated by direct ozone reaction with the biomass structure were detected. Ozone density was monitored during the ozonation by optical absorption spectroscopy. The optical results indicated that the ozone interaction with the bagasse material was better for bagasse particle sizes less than or equal to 0.5 mm. Both techniques have shown that the best condition for the ozone diffusion in the bagasse was at 50% of its moisture content. In addition, Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) were employed to analyze the lignin bond disruptions and morphology changes of the bagasse surface that occurred due to the ozonolysis reactions as well. Appropriate chemical characterization of the lignin content in bagasse before and after its ozonation was also carried out.

Removal of Ammonia from Water by Ozone Microbubbles

Ammonia is a major source of water pollution. One of the most common methods for removal of ammonia from water is oxidation. In this work, ozonation of ammonia using microbubbles was studied in a pilot plant. The experimental results indicate that ozone microbubbles were quite effective in oxidizing ammonia. Oxidation of ammonia was effective at high pH and high ozone generation rates. Ozonation was found to occur by direct reaction of ozone with ammonia at the higher pH. However, the hydroxyl radicals were also involved at the lower pH. Bromide ions acted as a catalyst in the ozonation process, and a faster rate of oxidation of ammonia and lower yield of nitrate was observed. The volumetric mass transfer coefficient of ozone in water was determined. It increased with the increasing rate of ozone generation and the pH of the medium.

Bromate Formation in Ozone and Advanced Oxidation Processes

Both the direct ozone reaction and the indirect hydroxyl radical reaction are important in ozonation of drinking water. This article investigates the effectiveness of ozone versus the advanced oxidation process of ozone coupled with hydrogen peroxide in the formation of bromate. The investigation was conducted on a pilot scale at various H2O2:O3 dose ratios of 0.1, 0.2, and 0.35 at different times of the year. The results of this study show a reduction in bromate with the addition of hydrogen peroxide to an ozone system versus ozone alone. It was also observed that bromate increased with increased H2O2:O3 ratios; however, concentrations were still lower than those in the ozone only system.

Ozonation of the reactive dye intermediate 2‐naphthylamine 3,6,8‐trisulphonic acid (K‐Acid): kinetic assessment, ozonation products and ecotoxicity

Ozonation of the commercially important, recalcitrant reactive dye intermediate 2‐naphthylamine 3,6,8‐trisulphonic acid (K‐Acid) was investigated. Ozonation performance was examined by following ozone absorption rates and K‐Acid, chemical oxygen demand and total organic carbon removals. Mean oxidation states and unidentified organic products were also determined. At pH 3, where direct ozone reactions are dominant, the second‐order rate constant between K‐Acid and molecular ozone was determined as 20 m−1 s−1 for steady‐state aqueous ozone concentration. The competition kinetics approach was also adopted where a reference compound, phenol, and K‐Acid were subjected to ozonation. By applying this method, the second‐order reaction rate constant was found to be 76 m−1 s−1. Common oxidation products formed during ozonation at pH 3, pH 7 and pH 7 with 1 mm hydrogen peroxide were identified as methoxy‐phenyl‐oxime, phenol, benzene, benzaldehyde and oxalic acid via high‐performance liquid chromatography and gas chromatography/mass spectrometry analyses. Continuous nitrate and sulphate evolution were observed during K‐Acid ozonation as a consequence of the abrupt release and subsequent oxidation of its amino and sulphonate groups. The number and amount of reaction products were most intensive for K‐Acid ozonation at pH 7 with 1 mm hydrogen peroxide. According to the acute toxicity tests conducted with Vibrio fischeri, ozonation products were not less toxic than the original K‐Acid solution that caused only 15% inhibition.

Effects of Operational Conditions on 1,4-Dioxane Degradation by Combined Use of Ultrasound and Ozone Microbubbles

1,4-Dioxane is regarded as a priority pollutant because it is hardly degraded by conventional methods of wastewater treatment. In this study, the degradation of 1,4-dioxane in water by the combined use of ultrasound and ozone microbubbles has been investigated. 1,4-Dioxane degradation by ultrasound and/or ozone followed a first-order reaction kinetics. The reaction constant for ozone microbubbles was higher than that for ozone millibubbles. The synergistic effect on reaction constant has been observed by the combined use of ultrasound and ozone microbubbles. The effect of hydroxyl radicals on reaction has also been investigated. Compared with the direct reactions of ultrasound and ozone, hydroxyl radicals play a major role in 1,4-dioxane degradation. The synergistic effect is enhanced with increasing ultrasonic input power and ozone concentration. Empirical equations of the relationships between ultrasonic input power, ozone concentration, and reaction rate constant have been established.

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.