Performance evaluation of ozonation and an ozone/hydrogen peroxide process toward development of a new sewage treatment process—Focusing on organic compounds and emerging contaminants

Performance of ozonation and an ozone/hydrogen peroxide process under a new concept centering on ozonation and/or ozone/hydrogen peroxide processes in sewage treatment processes comprising only physical and chemical processes are discussed, with focus on the removal of matrix organic compounds and emerging contaminants. Matrix organic compounds of filtrated primary sewage effluents were removed to as low as 3.2 mgC/L in the ozone/hydrogen peroxide process at an ozone consumption of around 400 mg/L. Linear relationships between ozone consumption and removal amounts of organic compounds were observed, in which the amounts of ozone required to remove 1 mg of organic carbon were 9.5 and 8.3 mg (2.4 and 2.1 mol-O₃/mol-C) in ozonation and the ozone/hydrogen peroxide process, respectively. Ratios of hydroxyl radical exposure to ozone exposure were in the order of 10^–9 to 10^–8 for ozonation and 10^–7 to 10^–6 for the ozone/hydrogen peroxide process. Experiments and a kinetic evaluation showed that ozonation and/or the ozone/hydrogen peroxide process have high elimination capability for emerging contaminants, even in primary sewage effluent with the thorough removal of matrix organic compounds. Newly found reaction phenomena, the temporal increase and decrease of dissolved ozone and accumulation of hydrogen peroxide in the early stage of oxidation with the continuous feeding of hydrogen peroxide, were presented. Possible reaction mechanisms are also discussed.     

1H NMR Study of Methyl Linoleate Ozonation.

Unsaturated fatty acids are essential components of vegetable oils and cellular membranes and the involved aspect of unsaturated fatty acids ozonation have been widely studied by different authors. In this paper, in vitro ozonolysis of unsaturated fatty acids with addition of water or ethanol has been studied by Proton Nuclear Magnetic Resonance (¹H NMR) at 250?MHz in order to explore the possibility of this technique for the detection of Criegee ozonides in characterizing ozone reaction with these substrates. The ozonolysis of methyl linoleate showed that signal intensities from formed ozonides were increased with ozone concentration increments. However, the signal intensities with addition of water were higher than those in ethanol addition. Signal intensities from olefinic double bonds were found to decrease with the increment in ozonide signals. Thus, a correspondence of the behavior of these signals is observed with a proportional rate reaction between the number of double bonds in the substrate molecule. Signals from aldehyde formation were poorly detected at lower ozone concentration. It was concluded that the evaluation of ozonide and olefinic double bond signals from 250?MHz ¹H NMR can be a useful tool in assessing ozone reaction with biomolecules. The reaction mechanism for the ozone reaction with unsaturated fatty acids in the presence of water or ethanol is analyzed.     

Distinct synergetic effects in the ozone enhanced photocatalytic degradation of phenol and oxalic acid with Fe3+/TiO2 catalyst

In this work, phenol and oxalic acid(OA) degradation in an ozone and photocatalysis integrated process was intensively conducted with Fe~(3+)/TiO_2 catalyst. The ferrioxalate complex formed between Fe~(3+) and oxalate accelerated the removal of OA in the ozonation, photolysis and photocatalytic ozonation process, for its high reactivity with ozone and UV. Phenol was degraded in ozonation and photolysis with limited TOC removal rates, but much higher TOC removal was achieved in photocatalytic ozonation due to the generation of ·OH. The sequence of UV light and ozone in the sequential process also influences the TOC removal, and ozone is very powerful to oxidize intermediates catechol and hydroquinone to maleic acid. Fenton or photo-Fenton reactions only played a small part in Fe~(3+)/TiO_2catalyzed processes, because Fe~(3+) was greatly reduced but not regenerated in many cases.The synergetic effect was found to be highly related with the property of the target pollutants. Fe~(3+)/TiO_2 catalyzed system showed the highest ability to destroy organics, but the TiO_2 catalyzed system showed little higher synergy.     

Systematic Analysis of the Biochemical Characteristics of Activated Sludge During Ozonation for Lowering of Biomass Production

Properties of activated sludge during ozonation were analyzed. The structure and surface characteristics altered with the increase of ozone dosage. At low ozone dosage, the floc structure was completely dismantled. Floc fragments reformed through reflocculation at an ozone dosage greater than 0.20 g O₃·g^?1 mixed liquor suspended solids (MLSS). Inactivation of microorganisms in the activated sludge mixture was caused by ozonation. Microbial growth decreased by up to 65% compared to the control. Simultaneously, 92.5% of nucleotide and 97.4% of protein in microbial cells of the sludge were released. Organic substance, nitrogen and phosphorus were released from the sludge during the ozonation process. The initial value of soluble chemical oxygen demand (SCOD) was 72 mg·L^?1. When the ozone dosage was 0.12 g O₃·g^?1 MLSS, the value of SCOD rapidly reached 925 mg·L^?1, increased by almost 12-fold. Simultaneously, 54.7% of MLSS was reduced. The composition of MLSS was changed, indicating that the inner water of cells and volatile organic substance decreased during the ozonation process.     

Degradation of Carbamazepine by Photo-assisted Ozonation: Influence of Wavelength and Intensity of Radiation

This article presents the results of an investigation into the function of UV in a photo-assisted ozonation process for treatment of carbamazepine (CBZ) in treated domestic wastewaters. Experiments were conducted on synthetic spiked water and secondary treated municipal wastewater. Degradation of CBZ was studied for various combination of O₃ dosage ranging from 4.8 to 14.4 mg/h and UV intensities with varying intensity and wavelength (UVC: λ = 254 nm and UVA: 352 nm). In synthetic spiked water, CBZ was degraded to below detectable limits within 0.5 min for ozone dose of 14.4 mg/h. The rate of degradation of CBZ increased exponentially with increase in ozone dose following a zero-order rate at each dose level. The degradation rate of CBZ in wastewater was slower compared to deionized water (DI) water by 40–75% for various doses of ozone, presumably due to the presence of organic matter remaining in treated wastewater. Optimal UV intensities for UVA and UVC were obtained as 0.62 and 0.82 mW/cm² for all doses of ozone in synthetic spiked water samples and UV intensities beyond this resulted in lower rates of degradation of CBZ. For photo-assisted ozonation with ozone doses of 9.6 and 14.4 mg/L, rate constants were two times higher for UVA irradiations as compared to UVC irradiation. Contrary to observations in DI water, experiments in wastewater showed increase in rate of degradation with higher UV intensities. Overall, photo-assisted ozonation was found to be appropriate for both water and wastewater treatment by exploiting the benefit of direct attack of ozone and of produced ^?OH radicals to yield a greater extent of mineralization of CBZ.     

Absorption kinetics of ozone in aqueous O-cresol solutions

The kinetics of ortho-cresol ozonation in water has been studied using the film theory. At most experimental conditions investigated, the kinetic regime of the absorption has been fast pseudo first order with respect to ozone. At 30°C mass transfer plays an important role in controlling the absorption rate of ozone. The selfdecomposition reaction of ozone does not take place because of the great reactivity of o-cresol with ozone. Reaction rate constants have been determined at pH 7 for different temperatures below 30°C. The following Arrhenius equation was obtained: k_T = 2.2 × 10²³ exp(-11784/T), L/mol ? s At temperatures below 30°C there exists an ozone partial pressure value above which the ozone absorption kinetic regime changes to fast second order regardless of experimental conditions.     

Enhancing Biodegradability of Textile Wastewater by Ozonation Processes: Optimization with Response Surface Methodology

ABSTRACT

In this study, an ozonation process was used to increase biodegradability of textile wastewater by considering chemical oxygen demand (COD) and color removal. Response surface methodology was applied in order to determine the significance of independent variables which are initial pH, reaction time and ozone dose. While a biological oxygen demand (BOD)/COD rate of 0.315 was obtained at optimum conditions, which are pH 9, 75 min of reaction time and 26 mg/L ozone dose, color and COD removal was obtained at 74% and 39%, respectively. BOD/COD ratio value increased from 0.18 to 0.32 by ozonation process. In addition, k coefficient for BOD also increased from 0.21 to 0.30 d^?1.     

Ozonation of unstretched natural rubber film from Hevea brasiliensis studied by ozone consumption and 13C NMR

Unstretched films of natural rubber (NR) from Hevea brasiliensis were exposed to ozone flow of 15 ml min^?1 from 4 to 300 min. The efficiency of reaction was determined by ozone consumption of NR films. Plots of reacted ozone mass versus film thickness show that the ozone penetration and the ozone reaction progressed into deeper layers (170 µm) than described in the literature (～0.5 µm). The previous proposed model based on viscometry measurements was corroborated by ozone consumption results. The effect of thickness on the O₃/NR stoichiometric ratio indicated that the diffusion process that controls the ozonation in unstretched film does not consist of the boundary progression behind which all reactive sites have been saturated. Ozonation in unstretched rubber film, while being less efficient than ozonolysis in solution, does have a reaction efficiency of the same order of magnitude. NMR spectroscopy was used to characterise the products formed by ozonation. Copyright © 2004 Society of Chemical Industry     

Effect of Ozone on Viability of Activated Sludge Detected by Oxygen Uptake Rate (OUR) and Adenosine-5′-triphosphate (ATP) Measurement

The current study focused on treatment of phenolic wastewater using an integrated process – dosing of ozone directly to activated sludge. The main goal was to analyze the effect of ozonation on viability of activated sludge in different systems – activated sludge in distilled water and activated sludge in wastewater. Two viability detection methods, oxygen uptake (OUR) rate and adenosine-5'-triphosphate measurement (ATP), were compared. The linear correlation between ATP and OUR measurements in studied range was found to be good (r² = 0.90). In case of ozonation of activated sludge in wastewater, ozone doses up to 42 mgO₃·gMLVSS^?1 did not influence the viability of sludge. In addition, contrary to ozonation of sludge in distilled water, soluble COD was reduced by 15.6% (at ozone dose of 42 mgO₃·gMLVSS^?1).     

Study of Ozonated Sunflower Oil Using 1H NMR and Microbiological Analysis

Prior studies have proven that ozonated vegetable oils present a high germicidal power. Ozonation of sunflower oil at different applied ozone dosage was carried out and peroxide and aldehydes indices along with antimicrobial activity were determined. The reaction products were identified using Proton Nuclear Magnetic Resonance Spectroscopy (¹H NMR). The principal signals intensity values were used for following the reaction course between ozone and sunflower oil. The reaction was following up to peroxide index values of 1202 mmol-equi/kg. The intensities of olefinic proton signals decreased with the gradual increase in ozone concentration but without disappearing completely. The Criegee ozonides obtained at 107.1 mg/g of ozone doses were approximately 3.9-fold higher than that at beginning of the reaction. The aldehyde protons were observed as a weak intensity signal in all the spectra. The signals belonging to olefinic protons from hydroperoxides appeared weak and increased with the increase in ozone doses. Signals from other oxygenated groups were assigned. The highest action spectrum of antimicrobial activity was obtained with the higher peroxide index. It was concluded that at higher applied ozone doses, the higher the antimicrobial activity potential of ozonized sunflower oil     

Ozone oxidation of β-lactam antibiotic molecules and toxicity decrease in aqueous solution and industrial wastewaters heavily contaminated

In this work, ozone oxidation of the antibiotics amoxicillin (AMX), cephalexin, and ceftriaxone was investigated in different samples: (i) aqueous solutions (100 mg L^?1), (ii) an industrial wastewater containing AMX at 125 mg L^?1 (chemical oxygen demand 6000 mg O₂ L^?1), and (iii) a heavily contaminated industrial wastewater containing the antibiotics at a total concentration of 320 mg L^?1. High performance liquid chromatography, molecular absorption spectrophotometry in the ultraviolet/visible region, and total organic carbon measurements showed that ozonation of antibiotics solutions led to removal higher than 95% with 10–20% mineralization. Industrial wastewater also showed very good efficiency for antibiotic removal (80–98%) after ozonation. Moreover, Microtox® test showed 86% toxicity reduction for the industrial wastewater.     

Pyruvic Acid Removal from Water by the Simultaneous Action of Ozone and Activated Carbon

Activated carbon (AC) has been used to catalyze the ozonation of pyruvic acid in water. Pyruvic acid conversions were found to be 9 and 37% after 90 min of single ozonation and single adsorption with 40 gL^?1 AC, respectively, while 82% was reached at the same conditions during the AC catalytic ozonation. Also, for similar conditions, mineralization reached values of 67% in the AC catalytic ozonation against hardly 5% in the non-catalytic experiment. The process likely develops through both adsorption of ozone and pyruvic acid on the AC surface and generation of hydroxyl radicals that eventually is the responsible oxidizing species. Rate constants for both non-catalytic ozonation and AC-Ozone catalytic surface reaction, at 20°C and pH 7.5, were found to be 0.025 min^?1 and 87.9 Lg^?1s^?1, respectively. For AC concentrations higher than 2.5 gL^?1 gas-liquid mass transfer of ozone constituted the limiting step. At lower concentrations, internal diffusion plus surface reaction controlled the process rate.     

Heterogeneous Catalytic Ozonation of Refinery Wastewater over Alumina-Supported Mn and Cu Oxides Catalyst

An economical method was proposed to develop an efficient alumina-supported manganese (Mn) and copper (Cu) oxides (Mn-Cu-O/Al₂O₃) catalyst with a high surface area, 184.06 cm² g^?1. The catalyst was utilized for degradation refinery wastewater by heterogeneous catalytic ozonation. The effects of various operating variables including pH, ozone and catalyst dosages, and temperature were systematically investigated in detail to obtain the optimized conditions for accelerated degradation of refinery wastewater. The optimum values were as follows: ozone dose 50.0 mg L^?1, catalyst dose 3.0 g L^?1, initial pH = 6.8, T = 17 °C. Refinery wastewater samples were analyzed by chemical oxygen demand (COD) and the results indicated that kinetics of COD followed a pseudo–first-order degradation. Moreover, hydroxyl radical mechanism rather than absorption was proposed, indicating that the surface hydroxyl groups were the active sites that played a significant role in catalytic ozonation.     

DECOMPOSITION OF 4-NITROPHENOL BY OZONATION IN A HOLLOW FIBER MEMBRANE REACTOR

The effect of initial pH, liquid flow rate, gas flow rate, and gaseous ozone concentration on the ozonation of 4-nitrophenol in a membrane reactor was investigated. The results showed that the disappearance of 4-nitrophenol increased with the increase of liquid flow rate, gas flow rate, and gaseous ozone concentration. The rise of the initial pH value led to an increase in 4-nitrophenol removal rate, but the increase became negligible after initial pH exceeded 9.5. The highest removal efficiency of 4-nitrophenol achieved was 94% after 100 min reaction when gaseous ozone concentration was 0.51 mmol L^?1, gas flow rate was 57 mL min^?1, liquid recirculation rate was 72 mL min^?1, and initial pH was 10.3. The membrane reaction system could be modeled based on the lumped kinetics of 4-nitrophenol removal, and the corresponding rate constant of 4-nitrophenol removal was determined from the model.     

Disinfection of recycled red‐meat‐processing wastewater by ozone

Ozonation of a real red‐meat‐processing wastewater was conducted in a semi‐batch reactor to explore the possibility of the water reuse. The experimental results revealed that ozone was very effective in disinfection of the red‐meat‐processing wastewater. After 8 min of ozonation with an applied ozone dose of 23.09 mg min^?1 liter^?1 of wastewater, 99% of aerobic bacteria, total coliforms and Escherichia coli were inactivated. Empirical models were developed to predict the microbial inactivation efficacy of ozone from the CT values for the real red‐meat‐processing wastewater. A correlation was also derived to estimate the CT values from the applied ozone dose and the ozone contact time. The results also revealed that under the ozonation condition for 99% inactivation of aerobic bacteria, total coliforms and E coli, the decrease in the chemical oxygen demand and the 5‐day biological oxygen demand of the wastewater were 10.7% and 23.6%, respectively. However, ozonation under this condition neither improved the light transmission nor reduced the total suspended solids (TSS) despite of the decolorization of the wastewater after ozonation. Copyright © 2005 Society of Chemical Industry     

Ozone treatment process for the removal of pharmaceuticals and personal care products in wastewater

This study investigated the degradability of pharmaceuticals and personal care products (PPCPs) by ozonation for the treatment of secondary effluent of a municipal wastewater treatment plant. A set of experiments were conducted in a laboratory using a pilot-scale process consisting of three flow-through reactors in series, by varying the ozone dose (1–9 mg L^?1), the hydraulic retention time (5–15 min), and the concentration of ozone injected into the reactors (14–42 mg L^?1). Thirty-seven PPCPs were detected in the secondary effluent, which belongs to the use categories of antibiotics, analgesics, antiarrhythmic agents, anticonvulsants, vasodilators, lipid modifying agents, anti-itch drugs, anti-psychotic drugs, insect repellents, bronchodilators, diuretics, peptic ulcer drugs, NMDA receptor antagonists, antifungal drugs, antimicrobial drugs, and antineoplastic agents. These PPCPs were broadly classified into five groups ranging from “sensitive” to ozone (O₃) or “unstable” in the ozonation process, to the group of “insensitive” to O₃ or “very stable” in the ozonation process. These groups are based on the PPCP concentrations after the ozone treatment and their limit of detection (LOD). Furthermore, this study examined comparatively the effects of the ozone dose, the retention (reaction) time, and the concentration of O₃ supplied to the reactors on the degradability of the PPCPs.     

Bio-Wax Latex-Modified Paper as Antimicrobial and Water-Vapor-Resistant Packaging Material

Beeswax and carnauba wax latex particles grafted with antimicrobial agents polyhexamethylene guanidine hydrochloride and polyhexanide were prepared by coupling reaction using N-(3-dimethylaminopropyl)-N’-ethylcarbodiimide hydrochloride as a coupling reagent. As a bifunctional agent for the surface treatment of paper the modified bio-wax latex improved the property of water-vapor resistance and antimicrobial activities of paper significantly after coating. Compared with the control sample the water vapor transmission rate (WVTR) of the paper with coating weight of 12 g/m² was reduced significantly from 2788.8 g/m²/d to 222.0 g/m²/d (BW-Gly-PHGH) thus demonstrating excellent water vapor barrier performance. The shaking flask method was utilized to investigate the antimicrobial activity against E. coli. The results showed that antimicrobial performance was improved substantially when the amount of added modified bio-wax particles was higher than 20 mg/g fiber. The bacterial inhibition ring test indicated that the antimicrobial mode of the modified bio-wax particles was likely based on the contact mode.     

Enterococcus sp. Inactivation by Ozonation in Natural Water: Influence of H2O2 and TiO2 and Inactivation Kinetics Modeling

This article presents the results about the disinfectant power of treatments based on the application of ozone (578 mg O₃ h^?1) and ozone combined with TiO₂ (1 g L^?1) and H₂O₂ (0.04 mM) on Enterococcus sp., a bacteria indicator used in the control of water quality. The results show that all the ozone-based treatments under study achieve the inactivation of Enterococcus sp. solution in natural water. Moreover, the combination of ozone with H₂O₂ or TiO₂ lightly improves the inactivation of Enterococcus sp. compared to the ozonation. However, the treatment with O₃, H₂O₂ and TiO₂ is less effective than the use of O₃, O₃/H₂O₂ or O₃/TiO₂. Finally, the primary mathematical models are applied (Hom, biphasic and Mafart) and they adequately describe the disinfection kinetics of the ozonation treatments studied for Enterococcus sp.     

Ozone/H2O2 Performance on the Degradation of Sulfamethoxazole

This work aims to analyze the contribution of H₂O₂ on ozonation of Sulfamethoxazole (SMX). A single ozonation was able to totally remove SMX. TOC and COD depletion rates after a transferred ozone dose of 60 mg/L was related to the formation and decomposition of H₂O₂. An increase on O₃ gas inlet concentration from 10 g/m³ to 20 g/m³ improved COD abatement from 11% to 36%. When the presence of H₂O₂ at the beginning of ozonation was tested, it was verified that COD and TOC degradation were enhanced, attaining maximum values of 76% and 32%, respectively, when compared with 35% and 15% reached in a single ozonation.     

Ozonation of chloronitrobenzenes in aqueous solution: kinetics and mechanism

BACKGROUND: Chloronitrobenzenes (ClNBs) are a family of toxic and bio‐resistant organic compounds. Ozone treatment is specifically suitable for partial or complete oxidation of non‐biodegradable components. However, few studies on the decomposition of ClNBs by ozone are available, and kinetics and mechanisms of ClNBs ozonation have not been thoroughly investigated. The kinetics and mechanism of ozonation degradation of ClNBs in aqueous solution were investigated, and the contribution of both molecular ozone and hydroxyl radicals was also evaluated. RESULTS: The results demonstrated that the decomposition of ClNBs was a pseudo‐first‐order reaction with respect to the pollutant concentration and the overall rate constant increased with an increase in pH. It declined, however, with an increase in pollutant and radical scavenger concentration. Furthermore, TOC removal rate was significantly lower than that of ClNBs, but the same order o‐ClNB < m‐ClNB < p‐ClNB was followed. Ozonation could not reduce TOC significantly, p‐chlorophenol, p‐nitrophenol, 2‐chloro‐5‐nitrophenol and 5‐chloro‐2‐nitrophenol were detected as primary degradation intermediates in ozonation of p‐ClNB. Rate constants of the direct reaction between ozone and ClNBs at 25 °C had been found to be lower than 1 M^?1S^?1. More than 95% of ClNBs removal was due to hydroxyl radical oxidation at pH ≥ 7. CONCLUSION: Advanced oxidation processes may be the preferred choice for the elimination of ClNBs from the environment. Copyright © 2008 Society of Chemical Industry