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.     

Activated sludge process coupled with intermittent ozonation for sludge yield reduction and effluent water quality control

BACKGROUND: Ozone is applied in wastewater treatment for effluent water quality improvement (post‐ozonation) as well as for excess sludge reduction (in the recirculation line). There is some evidence that ozone dosed directly to aerobic biooxidation (ABO) process enhances degradation of recalcitrant compounds into intermediates, following their biodegradation in the same reactor. However, no information regarding the influence of ozone on sludge yield in this system was found. Therefore, the current work aimed to evaluate the effect of ozone on the sludge yield when ozone is dosed directly to the ABO process. In addition, batch and continuous treatment schemes for phenolic wastewater treatment are compared. RESULTS: The results revealed that an optimal ozone dose of ～30 mgO₃ L^?1 day^?1 reduced the sludge yield by ～50%, while effluent water quality in terms of total chemical oxygen demand (TCOD), compared with a conventional ABO process, was improved by 35.5 ± 3.6%. Slight improvement in soluble COD removal at the same ozone dose was also detected. The toxicity of effluent water was reduced as the ozone dose was increased. CONCLUSIONS: In an integrated ozonation‐ABO process it is possible to simultaneously reduce sludge yield and to improve effluent water quality, as COD and toxicity are reduced. Copyright © 2011 Society of Chemical Industry     

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.     

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).     

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.     

Long Contact Time Ozanation For Swimming Pool Water Treatment

The elimination of contaminants in pool water through the “ozone – activated carbon process” is done stepwise. Sieving, flocculation and filtration steps are followed by ozonation. According to the German standards for the Treatment of Swimming Pool Water, the toxic ozone has to be removed from the water by filtration through an activated carbon layer before the water is brought back into the swimming pool. The treatment step is followed by chlorination for disinfection. In the ozone process described and in most of its modifications the time available for the reaction of the ozone is very short, usually 1.5 up to 3 min. First results with ozonation of model compounds, such as urea, creatinine, amino acids, etc., have shown–that the reaction rates are rather slow. Consequently, a longer reaction time leads to an improved decontamination of the swimming pool water. The efficiency of the ozonation process with longer reaction times followed by slower filtration has been proven in a research project, e.g. by experiments with the so–called “Ozone Combi Block^R – Process”. The potassium permanganate consumption and the combined chlorine as well as the formation potential of haloforms can be reduced effectively by elongated contact timeof ozone.     

Formation of oxygen structures by ozonation of carbonaceous materials prepared from cherry stones: II. Kinetic study

In this second part, the kinetics of the ozonation process of a char prepared from cherry stones (CS) is investigated. The char was obtained by heat treatment of CS at 600°C for 2 h in nitrogen. The effects of reaction time, partial pressure of ozone, and mass transport phenomena on the formation of oxygen complexes are studied. The surface chemistry of the samples was examined by FT-IR spectroscopy and the elemental chemical analysis was also determined for some samples. Results showed that the ozonation of the char led to oxygen chemisorption and to carbon gasification. The amount of oxygen complexes formed in the chemisorption stage (i.e., OH groups, CO structures, and ether structures) was found to be very sensitive to the increase in the ozonation time. The type of oxygen complexes was also time dependent. Ozonated products with relatively high concentrations of CO groups and ether structures were prepared by applying high ozone doses, whereas the formation of OH groups was favored at low ozone contents. The particle size did not influence the surface chemistry of the ozonated products. Only when the gas flow rate was lower than 40 l h⁻¹, restrictions to ozone mass transport developed. For kinetics of the char ozonation process, a mechanism based on the Langmuir-Hinselwood adsorption-desorption model was proposed, and the intrinsic reaction rates were calculated as a function of ozonation temperature. The activation energy for the ozonation stage of the char was equal to 41.6 kJ mol⁻¹.     

The Effects of Ozonation,Biological Filtration and Distribution on the Concentration of Easily Assimilable Organic Carbon (AOC) in Drinking Water

The concentration of easily assimilable organic carbon (AOC) as determined with growth measurements using wo bacterial cultures, increased linearly with ozone dosage at values below 1 mg O₃/mg of C. Moreover, a linear relationship was found between AOC increase and the decrease of UV absorbance of water after ozonation with various dosages. Biological filtration in water treatment reduced AOC concentrations, but the remaining values were above the AOC concentration before ozonation. This AOC removal was attended with an increased colony count in the filtrate. The AOC concentration of drinking water produced by the application of ozone in water treatment decreased during distribution. The greatest decrease was observed with the highest AOC concentration. Also in this situation, the highest colony counts were found. To date, ozonation is applied in seven water treatment plants in the Netherlands.     

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.     

A Comparison of Objectives,Level of Development and Energy Consumption of Two New Hungarian Ozonation Plants

Basedon the success of the first Hungarian large capacity drinking water treatment ozonation plant of Budapest that was put into operation in 1984, a similar second plant was put into operation in 1988 in Debrecen with 150,000 inhabitants. This recently built plant solves taste and odor problems and water quality development of a surface water treatment plant with a capacity of 50,000 m³/day that is operative for a longer period of time. The experiences gained at the Budapest ozonizing plant were utilized during both planning and construction. Thus, for example, the method of ozone absorption had been modified.

The in-situ repair of the Frings turbines for ozone contacting placed at the Rackeve plant of the Budapest Waterworks will be introduced, as well as a concept of a newer kind of ozone mixing.     

Investigation of gaseous ozone as an anti‐fungal fumigant for stored wheat

In this study, gaseous ozone was used as a fungicide to preserve stored wheat. The following operating parameters were investigated for their effects on the fungicidal efficacy of ozone: (1) the applied ozone dose; (2) ozonation time; (3) water activity of the wheat; and (4) temperature of the wheat. The effect of ozonation on germination of the wheat was also studied. Experimental results revealed that gaseous ozone was very effective in the inactivation of fungi associated with the wheat. Within 5 min of ozonation, 96.9% of the fungal spores were inactivated by applying 0.33 mg of ozone (g wheat)^?1 min^?1. It was also found that increases in both water activity and temperature of the wheat enhanced the fungicidal efficacy of ozone. In addition, results of this study indicated that the inactivation processes could be controlled by simply monitoring the ozone exiting from the reactor and, consequently, the time‐consuming microbial examination processes could be avoided. This finding would make the application of ozone in the preservation of cereal grains easier, simpler, and more cost‐effective. It was also found that although the applied ozone doses above certain thresholds may reduce the germination of wheat, the inactivation of fungi could be achieved using applied ozone doses far below those thresholds. Copyright © 2006 Society of Chemical Industry     

Compromise Between Bromate Ion Formation and Pesticides Degradation and/or Manganese Removal

Ozonation is a widely used technology within the water industry. Bromate ion formed by oxidation of water containing bromide ion was studied with the Gas Ozone Test and Pilot Scale Ozonation. Bromate ion formation was investigated along with the removal of triazines and/or manganese. Under identical conditions of ozonation, BrO₃ ^? formation is specific for each water and depends on parameters such as Total Organic Carbon, UV absorbance at 254 nm, applied ozone and ozone residual. Pesticides degradation by ozonation alone cannot be achieved without the formation of BrO₃ ^? at a high concentration. Hydrogen peroxide, at a constant ozone dose, reduces the BrO₃ ^? formation. However, even with the use of hydrogen peroxide, the concentration of BrO₃ ^? can remain in excess of the provisional Maximum Contaminant Level (10 μg/L). For certain types of water, pesticide degradation is difficult to achieve if the MCL for BrO₃ ^? has to be met. Manganese oxidation by ozone appears to be achieved without high bromate formation; indeed the presence of manganese hinders BrO₃ ^? formation.     

Ozone treatment of textile effluents and dyes: effect of applied ozone dose,pH and dye concentration

The ozonation of wastewater supplied from a treatment plant (Samples A and B) and dye‐bath effluent (Sample C) from a dyeing and finishing mill and acid dye solutions in a semi‐batch reactor has been examined to explore the impact of ozone dose, pH, and initial dye concentration. Results revealed that the apparent rate constants were raised with increases in applied ozone dose and pH, and decreases in initial dye concentration. While the color removal efficiencies of both wastewater Samples A and C for 15 min ozonation at high ozone dosage were 95 and 97%, respectively, these were 81 and 87%, respectively at low ozone dosage. The chemical oxygen demand (COD) and dissolved organic carbon (DOC) removal efficiencies at several ozone dose applications for a 15 min ozonation time were in the ranges of 15–46% and 10–20%, respectively for Sample A and 15–33% and 9–19% respectively for Sample C. Ozone consumption per unit color, COD and DOC removal at any time was found to be almost the same while the applied ozone dose was different. Ozonation could improve the BOD₅ (biological oxygen demand) COD ratio of Sample A by 1.6 times with 300 mg dm^?3 ozone consumption. Ozonation of acid dyes was a pseudo‐first order reaction with respect to dye. Increases in dye concentration increased specific ozone consumption. Specific ozone consumption for Acid Red 183 (AR‐183) dye solution with a concentration of 50 mg dm^?3 rose from 0.32 to 0.72 mg‐O₃ per mg dye decomposed as the dye concentration was increased to 500 mg dm^?3. © 2002 Society of Chemical Industry     

Advanced Water Treatment System of the Bureau of Waterworks,Tokyo Metropolitan Government

Since 1992, the Bureau of Waterworks, Tokyo Metropolitan Government (BWT) has introduced the advanced water treatment process, which is composed of ozonation and biological activated carbon treatment, within its service areas in a phased manner. The entire amount of water from the Tone River system has been treated by the advanced water treatment since 2014. The BWT currently has a capacity to treat approximately 5.5 million m³ per day using the advanced water treatment process. This report describes the progress of advanced water treatment facilities, the ozonation method, and the characteristic ozone diffusion devices used in Tokyo.     

Potential Ozone Applications for Water/Wastewater Treatment

Abstract

Several applications of ozonation were examined in this study for:

1. the treatment of stabilized high strength municipal landfill leachates,

2. the reclamation potential and toxicity reduction of municipal secondary effluents, and

3. the removal potential of phytoplanktons from surface waters.

The major parameters examined were the applied ozone dosage and the respective contact time. The application of single ozonation on leachates resulted in the efficient removal of color and organic loading, due to the respective oxidation, induced by ozonation. In addition, ozonation was found to be effective for the removal of the residual organic content of secondary municipal effluents. However, acute toxic effects after ozonation were observed on V. fischeri and were related to ozone concentration and contact time. Furthermore, the surface water used for drinking water production, was subjected to ozonation treatment for the removal of harmful cyanobacteria. Ozonation resulted in the reduction of the number of cyanobacteria species and in the breakage of the chain‐type species to cells with a lower number of atoms.     

Preliminary Investigation of Manganese-Catalyzed Ozonation for the Destruction of Atrazine

A preliminary experimental study conducted with a conventional bubble ozonation contactor column has shown that small amounts of Mn(II) greatly enhanced the destruction of atrazine by ozone. There is an inversely linear relationship between the dosed Mn(II) concentration and the residual ozone concentration at a specific reaction time. The ozone transfer efficiency into water is greater with the increase of Mn(II) dosage. Hydrous manganese dioxide prepared by reacting permanganate with manganese sulfate, also was shown to be effective in catalyzing the destruction of atrazine by ozone. The efficiency of catalytic activity for the destruction of atrazine caused by preformed hydrous Mn(IV) is slightly lower than the case of Mn(II). A lower residual ozone value using manganese dioxide compared to the case of ozone alone suggests that ozone also may be decomposed by hydrous Mn(IV). However, a commercial MnO₂ did not show any catalytic activity for atrazine destruction. The very much greater degree of atrazine oxidation by manganese-catalyzed ozonation compared to ozone alone is speculated to be the result of the generation of highly oxidative intermediate species such as hydroxyl radicals during the reaction between ozone and manganese species.     

Feasibility of Sludge Ozonation for Stabilization and Conditioning

A pilot-scale sludge treatment plant was built to investigate the feasibility of ozonation processes for waste activated sludge treatment. Ozonation of wastewater sludge resulted in mass reduction by mineralization as well as by supernatant and filtrate recycle. Another advantage of sludge ozonation is a significant improvement of settleability and dewaterability. Experimental results showed that mass reduction of 70% and volume reduction of 85% compared with the control sludge was achieved through the sludge ozonation at a dose of 0.5?gO₃/gDS. It is also interesting to note that the filterability deteriorates up to ozone dose of 0.2?gO₃/gDS and then improves considerably at a higher ozone dose. The filterability could be improved by chemical conditioning even at a low ozone dose. The economic feasibility by cost analysis reveals that ozonation processes can be more economical than other alternative processes for sludge treatment and disposal at small-sized wastewater treatment plants.     

Mathematical Modeling and Simulation of Ozonation Processes in a Downstream Static Mixer with Sieve Plates

New standards for drinking water disinfection require better optimization of the ozonation stage on the basis of the concentration×contact time (CT) concept, and production of ozone from pure oxygen at higher concentrations presumes application of the new type of contactors operating efficiently at lower gas/liquid volumetric ratios. One possible construction to meet these requirements is a downstream static mixer with sieve plates. At higher flow rates of liquid in this mixer, the interfacial area may reach 10,000m²/m³ at energy dissipation 1–5kW/m³. Due to the very intensive hydrodynamic regime the ozone utilization degree in the gas phase reaches 98–100% in natural lake water ozonation. Mathematical simulation of lake water ozonation in this mixer indicated that the process proceeds mostly in the diffusion or kinetic regime depending on the operating parameters. The dominating parameters besides the sieve geometry are the liquid flow rate in the holes of the sieves and the volumetric liquid/gas ratio.     

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.     

Survival of Bacteria After Ozonation

The change of the bacterial population after each water treatment process was examined in a full-scale water treatment plant that uses ozone as a primary disinfectant. The fluctuation of heterotrophic bacterial number along the water treatment processes was determined. After ozonation, the bacterial number decreased to 13 CFU/mL. The surviving bacteria after each water treatment process were identified to genus or species level. The significant finding was the predominance of double-layered gram-positives (75%) among the surviving bacteria after ozonation. It included Mycobacterium spp., Bacillus spp., Corynebacterium spp., and Micrococcus spp. On the other hand, the dominance of gram-negatives was observed in most other water samples but each treatment process exerted different selection on dominant bacterial groups. The proportion of opportunistic pathogens was the lowest in the ozonated water.