Applications of Ozone Decomposition Models

Simulated ozone decomposition profiles in “pure” water were made using two analytical kinetic ozone decomposition models and contrasted with experimental and literature data. Fundamental and applied applications of ozone consumption models are presented, demonstrating the importance of both direct and indirect oxidation of inorganic and organic species. A novel approach to simulating ozone decomposition in the presence of natural organic matter (NOM) is presented, concluding that NOM predominantly behaves as a direct consumer of ozone and promoter of ozone decomposition.     

Ozonation of VOC's in the Presence of Humic Acid and Soils

The oxidation of several VOCs in the presence of humic acid and soil is described in this paper. It was found that while ozone does react appreciably with humic acid, as indicated by significant changes in the spectral characteristics of humic acid, the TOC levels in these solutions changed by only 3‰ or less. The oxidation of four olefinic VOCs occurred in solutions containing up to 120 mg/L humic acid, however, the extent to which each of the compounds reacted is very much compound specific. The effect of pH and ozone dosage on these reactions was considered. The effects of pH were weak for all compounds except trichloroethane. Ozone dosage had a significant effect on the extent to which each of the VOCs was oxidized, although no simple relationship between ozone dosage and the amount of VOC which reacted could be obtained. Complete oxidation of dy–dichloroethylene by ozone (22 mg/L) occurred in solutions containing 1.0 g of Eustis soil suspended in 10.0 mL water. However, only 40‰ oxidation of tetrachloroethylene was achieved using an ozone dosage of 17.3 mg/L when 1.0 g of Eustis soil was present. The results obtained in this study strongly suggest that the influence of free radicals, generated during the decomposition of ozone, on the oxidation of VOCs is significant. The work described here suggests that ozone may be applicable for the treatment of contaminated soils and waters containing high concentrations of matter.     

Oxidation of Organic Pollutants of Water to Mineralization by Catalytic Ozonation

The oxidation of various organic compounds in aqueous solution was studied using catalytic ozonation (TOCCATA process) and conventional ozonation. The aim of the work is to assess catalytic ozonation efficiency for the mineralization of various organic compounds in order to envisage its application on real effluents. The selected organic compounds (about 30) are commonly found in industrial wastewaters. Comparative experiments were performed in batch mode at laboratory scale. Investigations were focused on ozone consumption rate, variations of total organic carbon, oxidation by-products and oxidation rate. Catalytic and conventional ozonation treatments were compared considering kinetic data, mineralization extent, and effect of organic functionalities. Catalytic ozonation system according to the TOCCATA process was able to convert organic compounds which were totally inert to ozone treatment and permitted considerably enhanced reaction rates when compounds were reactive to ozonation.     

Treatment Efficiency of an Improved Ozonation Unit Applied to Fish Culture Situations

Ozonation has been successfully applied in experimental fish culture recirculation systems, especially to oxidize some of the most important metabolites (such as nitrite, ammonium, BOD) at times when these concentrations reach a daily peak level. In this study the oxidation rates for ammonium, nitrite, and BOD have been determined for each of these components separately or in combination, using an improved design of the contacting chamber. Two flow rates and three ozone concentrations were employed. Ammonia oxidation rates were slowest while nitrite and BOD removal was rapid. Ozone concentrations substantially influenced the oxidation rates for ammonium ion. Nitrate was oxidized equally rapidly under almost all operational conditions. Slight differences in oxidation rates were noted for both ammonia and nitrite as long as the BOD was high.     

Effects of Ozone and Ozone/Hydrogen Peroxide on the Degradation of Model and Real Oil-Sands-Process-Affected-Water Naphthenic Acids

Naphthenic acids (NAs) are persistent compounds that contribute to the toxicity of oil sands process-affected water (OSPW). In this study, the effects of ozone and ozone/hydrogen peroxide on the NAs degradation in buffered water and OSPW were examined. Cyclohexanoic acid (CHA) was used as a model NAs compound in buffered water experiments at two different pHs, using radical scavengers. At pH 9, the addition of carbonate did not have any effect on CHA degradation. Additions of tert-butyl alcohol and tetranitromethane decreased the CHA degradation levels. For the OSPW experiments, degradation of acid-extractable fraction (AEF) and NAs was examined. Approximately 90% of AEF was oxidized in a semi-batch system. In a batch system, 99% of OSPW NAs were degraded. This study demonstrated that ozone and ozone/hydrogen peroxide could be suitable treatment processes for OSPW remediation.     

Ozonation of Drinking Water: A Design Methodology

The formation of potentially carcinogenic organic halides has been shown to result from drinking water disinfection with chlorine. xidative treatment of organic halide precursors with ozone prior to chlorination has surfaced as an attractive technique for reducing the formation of these compounds. In addition to reduction of precursor levels, preozonation has been reported to effect other beneficial results in water treatment. This paper presents design methodologies to optimize the implementation of the ozonation process for water treatment applications. Pre-design considerations common to all ozonation design processes are discussed. Subsequently, design procedures for the ozone generation and contacting systems are reviewed.     

Mass Balance Analysis of Ozone in a Conventional Bubble Column

Ozone transfer into potable water was studied in a conventional bubble column, and ozone mass balances have been calculated to determine ozone utilization efficiencies. Liquid and gas flow rates, as well as inlet ozone concentrations in the gas phase were varied. Using these data, it was possible to determine the ozone mass transfer coefficient, ozone transfer efficiency, and ozone consumption. A model of ozone transfer was established, and procedures for calculating the optimum design parameters and operating conditions are proposed.     

Ozone Degradation of Cyclophosphamide – Effect of Alkalinity and Key Effluent Organic Matter Constituents

The influence of three effluent organic matter (EfOM) model compounds (alginic acid, peptone and natural organic matter-NOM) and alkalinity on the ozonation of cyclophosphamide (CPD) was investigated. The rate of ozone decay increased with increasing model compounds concentration in the order of peptone > NOM > alginic acid. Increasing alkalinity inhibited ozone decay at all concentrations of alginic acid and at low concentrations of NOM and peptone (DOC < 3 mg/L), while at high NOM and peptone concentrations the effect of alkalinity on ozone decay was minor. Presumably, ozone decay was mainly controlled by direct reaction with these two model compounds, resulting in ?OH (hydroxyl radical) formation yield of 29% and 19%, for peptone and NOM respectively. In the presence of alginic acid ?OH formation through a radical chain reaction resulted in a yield of 30%. Cyclophosphamide (CPD) removal decreased with increasing alkalinity and model compounds concentration (most pronounced for peptone and less pronounced for alginic acid); most likely due to increase in the scavenging effect on ?OH.     

Decoloration of acid dye effluent with ozone: effect of pH, salt concentration and treatment time

A study of the ozone treatment of textile effluent containing acid dyes has been carried out to explore the influence of their chemistry, and the pH, salt concentration, ozone dose and time of treatment. The experiments were constructed using a Box-Hunter second-order composite design for three variables. The study has demonstrated that the type of aromatic rings and the number of sulphonic acid groups in the dye have a marked effect on decoloration. The pH, salt concentration and treatment time are also found to have a predictable influence. The ozone oxidation of acid dye effluent results in a reduction in pH and total organic carbon content.     

无机盐对乳状液稳定性和转相的影响

在进行化学驱油尤其是表面活性剂驱油的过程中,油藏地层水中含有的无机盐离子会对表面活性剂的乳化等性能产生影响。使用0.4%（质量分数）的十二烷基苯磺酸钠（SDBS）作为乳化剂与原油制备了水包油型乳状液,通过向SDBS溶液中加入不同浓度的共13种无机盐,考察了这些无机盐对水包油型乳状液稳定性和转相的影响。实验结果表明：钠盐和钾盐均存在最佳盐质量浓度,在此质量浓度下乳状液稳定性增强,没有引发乳状液转相;二价和三价无机盐不利于乳状液的稳定,其引发乳状液发生转相的能力依次为氧化铝＞氯化铁＞氯化钡＞氯化锶＞氯化钙＞氯化镁;处于最佳盐质量浓度时,弱碱性钠盐可与SDBS产生协同效应,有利于乳状液的稳定。     

Ozonation of Sulfur-Containing Aliphatic Compounds in Aqueous Solution. I

In view of the possible reaction of ozone with sulfur containing natural and anthropogenic compounds, the oxidation products of sulfur-containing aliphatic model compounds in pure water in dependence on pH value were investigated.

In the first part, as a model compound for thioether, thiodiglycolic acid was investigated. The rate of elimination is independent of pH-value. At pH 3 as primary product thionyldiglycolic acid is formed, which undergoes further oxidation, but very slowly, to sulfonediacetic acid, which is very stable against ozone attack at pH 3. At pH 7 and higher, however, thionyldiglycolic acid is oxidized faster to sulfonediacetic acid, and this compound is oxidized to sulfoacetic acid, oxalic acid, glyoxylic acid, sulfateion, and CO₂ after longer reaction times. In all cases, sulfite as an inorganic intermediate product could not be identified. Also the intermediate products in pure solutions are ozonized. The mass balances show that 90 to 95% of the oxidation products could be identified. Based on these results, reaction schemes are discussed.     

Combination of Dyeing Method and Ozone After-Treatment to Apply Natural Dyes on to Cotton Fabrics

The textile industry has an important place in global marketing and trade. Both production and consumption of cotton and cotton-based materials were also considerably important. Until now, the essential term for the textile industry can be summarized as product diversity. However, today, in addition, the demand for natural and organic products has been in an increasing trend. In this respect, the use of natural dyes has become popular again. However, the need to use mordants, especially metal salts, is the most important dilemma in terms of natural production. This study was aimed to show the usability of ozone gas with natural dyeing and to introduce an alternative production that avoids use of mordants. It was observed that different ozone gas applications can be used to obtain color diversity from the same natural dye source, which at present is achieved by using different mordants. On the other hand, for the tested dyes, different fastnesses were analyzed in terms of the effect of ozone gas treatment style and different mordants. It was found that in general the tested natural dyes have good fastness values except for light fastnesses. The use of ozone gas only improved the wet rubbing fastness values when ozone gas was applied directly to the wet dyed sample. For other fastnesses, ozone did not show any significant effect.     

Optimization of Ozonation Process for a Composting Leachate-Contaminated Soils Treatment Using Response Surface Method

The ozonation process has become one of the most favorable processes among soil remediation technologies nowadays. Ozone, which has an oxidation potential of 2.07 V and acts as a powerful oxidizer, is capable of degrading organic pollutants of soil in a short period of time without producing any toxic residuals. In this study the capability of ozone, as an ex-situ method of soil treatment, in remediating the leachate-contaminated soil has been investigated. To maximize the removal efficiency of organic content of soil, design of experiments using the response surface method (RSM) and central composite design (CCD) have been employed. To select the range of effective parameters several experiments were performed at laboratory scale. Results showed a range of effective parameters on the ozonation process, including pH, humidity, and initial soil pollution. Present research shows that acid-washed ozone greatly enhanced the removal efficiency. According to the developed model, the maximum removal efficiency using acid-washed ozone was obtained by setting the parameters as pH = 10.8, humidity of 5% and initial organic content of soil to be 7720 mg/kg. Confirmation experiments showed that RSM could be effectively utilized for the optimization of the ozonation process. Analysis of variance also showed that pH was the most significant factor affecting removal efficiency.     

Ozonation and Advanced Oxidation of Wastewater: Effect of O3 Dose,pH, DOM and HO•-Scavengers on Ozone Decomposition and HO• Generation

The decomposition of ozone in wastewater is observed starting 350 milliseconds after ozone addition. It seems not to be controlled by the autocatalytic chain reaction, but rather by direct reactions with reactive moieties of the dissolved organic matter (DOM). A larger ozone dose increases ozone consumption prior to 350 milliseconds but decreases the rate of ozone decomposition later on; this effect is predicted by a second-order kinetic model. Transferred Ozone Dose (TOD) is poorly correlated with ozone exposure (= ∫[O₃]dt) indicating that TOD is not a suitable parameter for the prediction of disinfection or oxidation in wastewater. HO^? concentrations (> 10^?10 M) and R_ct (=∫[HO^?]dt/∫[O₃]dt > 10^?6) are larger than in most advanced oxidation processes (AOP) in natural waters, but rapidly decrease over time. R_ct also decreases with increasing pre-ozonation doses. An increase in pH accelerates ozone decomposition and HO^? generation; this effect is predicted by a kinetic model taking into account deprotonation of reactive moieties of the DOM. DOC emerges as a crucial water quality parameter that might be of use to normalize ozone doses when comparing ozonation in different wastewaters. A rapid drop of absorbance in the water matrix—with a maximum between 255–285 nm—is noticeable in the first 350 milliseconds and is directly proportional to ozone consumption. The rate of absorbance decrease at 285 nm is first order with respect to ozone concentration. A kinetic model is introduced to explore ozone decomposition induced by distributions of reactive moieties at sub-stoichiometric ozone concentrations. The model helps visualize and comprehend the operationally-defined “instantaneous ozone demand” observed during ozone batch experiments with DOM-containing waters.     

Advanced Oxidation and Degradation of Vinyl Chloride in Water

A kinetic model has been developed for the degradation of organic pollutants, by considering both the decomposition of ozone molecules and the interaction between ozone and hydrogen peroxide in the formation of a hydroxyl radical, and the subsequent reactions. Rate equations were derived for the depletion of ozone and pollutants in the advanced oxidation processes (known as the peroxone oxidation). Experiments were carried out at 298 K in the pH range 3 to 11. Kinetic data obtained experimentally from the hydrogen peroxide‐ozone reaction and advanced oxidation of vinyl chloride were analyzed by using the proposed rate equations, indicating that the depletion rate of ozone increases with the concentrations of ozone, hydrogen peroxide, and hydroxyl ion, as predicted by the kinetic model.     

Degradation of Endocrine Disrupting Chemicals by Ozone/AOPs

The presence of endocrine-disrupting compounds (EDCs) in the aqueous environment is of increasing concern due to their adverse impact on aquatic life, and potential risk to human health. Among the EDCs of concern are steroidal estrogenic hormones such as estrone (E1), 17β-estradiol (E2), estriol (E3), and 17α-ethinylestradiol (EE2), which have a high environmental prevalence and strong estrogenic activity. In addition, the extensive use of alkylphenol ethoxylates (AP_nEOs), bisphenol A (BPA) and phthalate compounds have resulted in an environmental presence at significant concentrations, although they appear to have a lower estrogenic activity than the steroidal hormones. As water and wastewaters are some of the primary routes of exposure to EDCs, it is important to determine at what levels EDCs are found in these media and how these levels may be reduced. Hence, it is necessary to understand the fate of EDCs in conventional water and wastewater treatment plants, as well as the efficacy of more specialized treatment methods, such as adsorption and oxidation. This paper is a summary of the latest information on the degradation of prominent EDCs by ozone and ozone-based advanced oxidation processes (AOPs). From this review, it is clear that ozone and AOPs are effective in degrading these EDCs, with the possible exception of phthalates, which are relatively stable to ozone oxidation. Knowledge of the formation of reaction products from the treatment by ozone and AOPs is relatively poor at present, and particularly for the non-steroid compounds.     

废水中氨及甲苯的O3／H2O2氧化降解及其动力学

研究了废水中的无机污染物氨和有机污染物甲苯在Ｏ３／Ｈ２Ｏ２ 中的氧化降解过程。根据Ｏ３／Ｈ２Ｏ２ 反应产生自由基ＯＨ·的机理和污染物在Ｏ３／Ｈ２Ｏ２ 中的氧化降解过程,推导出污染物被Ｏ３／Ｈ２Ｏ２氧化降解时的动力学模型,实验结果与理论模型相符。     

Ozone Treatment of Secondary Effluent at U.S. Municipal Wastewater Treatment Plants

Ozone is a strong oxidant used to treat a variety of constituents in potable water, wastewater, water reuse, and industrial water treatment applications. Ozone is effective at oxidizing a wide range of organic and inorganic compounds and disinfection. Well-known in potable water treatment, with about 400 US installations and 3,000 world-wide, ozone has limited application at wastewater treatments, with less than 10 operating facilities in the US. The ability of ozone to significantly reduce low level concentrations of trace organic compounds, including endocrine disrupting chemicals (EDCs), pharmaceuticals and personal care products (PPCPs), and other emerging contaminants have increased interest in applying ozone in potable water and wastewater treatment. Treating at the point source discharge rather than the water supply intake may be more effective. A recent American Water Works Research Foundation (AwwaRF) report indicated high removals of many EDCs and PPCPs at typical disinfection doses. Several wastewater utilities have installed or are in the process of installing ozone to treat secondary effluent. These utilities are using ozone in a variety of ways: as a primary disinfectant, for treatment of microconstituents, and in combination with other processes (e.g. membranes and UV) to produce high-quality water for indirect potable reuse (IPR). The different applications, treatment goals and basis of process selection are compared and contrasted. Secondary benefits of ozone treatment of secondary effluent, including the use of off-gas in biological treatment is also discussed.     

Formation of Oxamic Acid During Drinking Water Treatment

Although oxamic acid has been identified as an ozone oxidation product from several precursor compounds, concentrations for drinking water have not been published previously. This study shows results from a full-scale drinking water treatment plant, noting that the mean concentrations for oxamic acid reached 21.3 μg/L after ozonation and prior to filtration. Subsequent multiple-layer filtration removed 85% of oxamic acid on average, and mean concentrations in drinking water were 2 μg/L. Up to 5.9% of the oxamic acid found in ozone-treated groundwater may be formed from Chloridazon metabolites.     

A Comparative Study: Degradation of 2,5-Dichlorophenol in Wastewater and Distilled Water by Ozone and Ozone-UV

The effectiveness of ozone and ozone-UV processes on effluents containing chlorophenol was evaluated. Experiments were performed using 3.06 mM of 2,5-dichlorophenol in distilled water and wastewater at pH 7 with ozone dose of 37 mg/L. An ozone dose of 1.2 g/h was effective in completely degrading 2,5-dichlorophenol and reducing the toxicity of its by-products. Overall, ozone-UV process was more effective in the oxidation of 2,5-DCP. Ozone-UV treatment of wastewater showed the highest mineralization (53%), dechlorination (100%), COD removal (75%), and biodegradability (BOD₅/COD = 0.85). The organic/inorganic matters in wastewater seem to have a positive effect on the oxidation of 2,5-DCP and supports the use of ozone and ozone-UV processes for industrial effluent treatment.