Effect of Ozonation on Trihalomethane and Haloacetic Acid Formation and Speciation in a Full-Scale Distribution System

Disinfection by-product (DBP) formation was evaluated before and after ozone implementation at two full-scale drinking water facilities in Las Vegas, NV USA. The two treatment plants used preozonation for primary disinfection followed by direct filtration with subsequent chlorination for secondary disinfection. DBP data was evaluated from the finished water of the two treatment plants along with six locations in the distribution system. Results showed that preozonation reduced the formation of total trihalomethanes (TTHM) by up to 10 μg/L and the sum of five haloacetic acids (HAA5) by up to 5 g/L. These reductions were primarily due to decreases in the di- and trichlorinated DBPs such as chloroform, bromodichloromethane, and trichloroacetic acid. Ozonation appeared to shift the speciation of TTHMs and HAA5 to favor increased formation of the di- and tribrominated species such as bromoform, chlorodibromomethane, and dibromoacteic acid. A bromide mass balance showed that <30% of the raw water bromide was accounted for by the formation of TTHMs (8–21%), HAAs (2–3%) and bromate (5%). Reducing the concentration of THMs and HAAs is often not the primary purpose of ozonation, but it can assist utilities in meeting regulatory requirements during drinking water treatment.     

Effective Ozonation of Secondary Effluents with Initial Ozone Demand

It is clarified that the ozone consumption during the initial stage of ozonation before dissolved ozone appears is the same value as that during the initial 20 seconds in batch mode experiment. This initial ozone consumption was defined as initial ozone demand (IOD) in this study. IOD of secondary effluent was shown to be 0.3–0.5 mgO₃/mgC₀. More than 90% of 17β-estradiol (E2) was reduced, and formation of ozonation by-products was controlled within this ozone demand. This state can be also characterized by reduction of the values of UV₂₅₄, fluorescence intensity at 345 nm (Excitation)/435 nm (Emission) and that at 240 nm/435 nm to 0.06 /cm, 35 and 15, respectively.     

Advanced treatment of textile dyeing wastewater through the combination of moving bed biofilm reactors and ozonation

A four-stage lab-scale treatment system [anaerobic moving bed biofilm reactor (MBBR)-aerobic MBBR-ozonation-aerobic MBBR in series] was investigated to treat textile dyeing wastewater. The MBBRs were operated in a continuous horizontal flow mode. To determine the optimum operating conditions, the effect of hydraulic retention time (HRT) and ozonation time on pollutant removal were analysed by continuous and batch experiments. The optimum operating conditions were found to be 14 h HRT for both anaerobic and no. 1 aerobic MBBRs, 14 min ozonation time and 10 h HRT for no. 2 aerobic MBBR. The average influent concentrations of chemical oxygen demand (COD), suspended solids (SS), ammonia and colour were 824 mg/L, 691 mg/L, 40 mg/L and 165°, respectively. Under these conditions, the average effluent concentrations of COD, SS, ammonia and colour were 47 mg/L, 15.2 mg/L, 5.9 mg/L and 6.1°, respectively, corresponding to total removal efficiencies of 94.3%, 97.8%, 85.3% and 96.3%, respectively. The final effluent could meet the reuse requirements of textile industry. The anaerobic MBBR process improved the biodegradability of the raw wastewater, while the two aerobic MBBRs played an important role in removing COD and ammonia. The ozonation process enhanced the biodegradability of no. 1 aerobic MBBR effluent, and finally, deep treatment was completed in no. 2 aerobic MBBR. The combined process showed a promising potential for treatment of high-strength dyeing wastewater.     

How Bromate and Ozone Concentrations Can be Modeled at Full-Scale Based on Lab-Scale Experiments – A Case Study

This article presents a full-scale modeling study of an industrial ozonation unit for practical application. The modeling framework combines an integrated hydraulic model (systematic network) with a quasi-mechanistic chemical model. Dealing with natural water, the chemical model has to be parameterized, and the parameters calibrated. This was done based on lab-scale experiments. The calibration results showed that the chemical model is able to account for changes in contact time with ozone, pH, temperature, ozone dose, NOM concentration, bromide concentration. Comparison of residence time distributions showed that the hydraulic model accurately reproduces flow conditions. Six sampling points were installed along an industrial ozonation unit of 487 m³ consisting of two baffled tanks in series. Bromate and ozone concentrations were monitored under varying operational process conditions. After the selection of a value for the k_La, simulations were run. Using the lab-scale calibrated models, simulated and experimental data were found in close agreement: 84% of the simulated concentrations for ozone matched measurements (±experimental error), 60 % for bromate. A readjustment of the kinetics of a single reaction (out of 65) showed that seasonal changes in NOM activity may easily be taken into account based on regular concentration measurements (90% of the bromate concentrations were then modeled accurately).     

Using catalytic ozonation and biofiltration to decrease the formation of disinfection by-products

The effect of catalytic ozonation in a fluidized bed reactor (FBR) on the formation of individual disinfection by-products (DBPs) was investigated. A biofiltration column was used to evaluate the removal efficiency of biotreatment on DBP precursors. Dissolved organic carbon (DOC), simulated distribution system trihalomethanes (SDS THMs), and six simulated distribution system haloacetic acids (SDS HAA6) were monitored. The source water was polluted by domestic and agricultural effluents. Catalytic ozonation removed the concentration of DOC by 8.2-51.4% depending on the dosage of the catalyst. The decreases of SDS THMs and SDS HAA6 were 41.3-51.2% and 31.7-48.3%, respectively, under the same operating conditions. Biotreatment greatly improved the removal efficiency of DOC and decreased the formation of DBPs. Up to 81.7%, 76.1%, and 81.3% of DOC, SDS THMs precursors, and SDS HAA6 precursors were removed after the catalytic ozonation followed by biofiltration, respectively. The treatment processes also influenced the proportions of individual DBP species. The proportion of bromine-containing species from the SDS THMs and SDS HAA6 increased in water samples after being treated by biofiltration alone, ozonation alone, catalytic ozonation, and catalytic ozonation followed by biofiltration.     

Evaluation of Decolorization,Mineralization, and Toxicity Reduction of Tropaeolin O in Water by Ozonation with UV Irradiation

The combination of ozonation with UV irradiation can remove Tropaeolin O (AO6) and its by-products effectively and completely. The ozone dose affects the rate of decolorization, AO6 species removal, and dissolved organic carbon (DOC) reduction significantly. After 240 minutes of ozonation, the average DOC removal efficiency (η_DOC) for O₃ alone was about 0.79, while η_DOC for O₃/UV was 1.0. The average DOC removal rate was low at early stage of ozonation due to decolorization and low DOC. At later stage of ozonation, average DOC removal rate decreases because of the formation of persistent intermediates. The ozone consumption was consistent with η_DOC. The ratio of ozone consumption to ozone applied decreased from 14 to 12% when η_DOC < 40% because the decolorization in the early stage of the ozonation of AO6 may consume a relatively large amount of ozone. It was found that NO₂, NO, CO₂, and small amount of SO₂ was detected in the off-gas. The effective concentration (EC50) increased from 23.48% to 100%, suggesting that the toxic reduction was achieved, and O₃/UV system was superior to O₃ alone system     

Pilot-Scale Evaluation of Ozone vs. Peroxone for Trihalomethane Formation

Both the direct ozone reaction and the indirect hydroxyl radical reaction are important in the ozonation of drinking water. This paper investigates the effectiveness of ozone versus ozone coupled with hydrogen peroxide (peroxone) with respect to trihalomethanes formation. The investigation was conducted on a pilot-scale at various H₂O₂:O₃ dose ratios of 0.1, 0.2, and 0.35 and change in peroxide addition point (pre- and post-ozonation). It was observed that the addition of peroxide, either before or after ozonation, increased trihalomethane concentrations and that increasing H₂O₂:O₃ increased trihalomethane concentrations. In comparing the addition point of peroxide, addition prior to ozonation better controlled trihalomethane formation than after ozonation.     

Biological Nitrogen Removal Using the Supernatant of Ozonized Sludge as Extra Carbon Source

A sludge ozonation process with lab-scale anaerobic/oxic (A/O) system was used to investigate the utilization of the ozonized sludge (OS) supernatant as extra carbon source for denitrification. The optimal ozone dose for the sludge ozonation was 0.2 gO₃/gSS. The concentrations of SCOD, BOD, NH₃-N and TN in the supernatant increased respectively at this ozone dose. In the meantime, the sludge was significantly reduced. The OS supernatant had negative effect on nitrification because of low pH and alkalinity. After alkalinity adjustment, the A/O with the OS supernatant as the extra carbon source achieved a nitrogen removal rate of 78%, which was very close to the control experiment using glucose (79%).     

Sludge Ozonation and its Application to a New Advanced Wastewater Treatment Process with Sludge Disintegration

The applicability of sludge ozonation on wastewater treatment processes was investigated to reduce the amount of excess sludge without losing phosphorus removal efficiency. Solubilization degree per ozone consumption for general sludge was in the range from 2.4 to 5.8 gSS/O₃ and from 4.1 to 7.7 gCOD/gO₃. Around 80 to 90% of solubilized organics was biodegradable at a solubilization degree of 0.3. Based on the experimental results, a lab-scale plant with sludge ozonation and phosphorus crystallization was constructed to investigate the treatment performance. Amount of excess sludge was reduced by 93% with almost complete removal of soluble BOD and phosphorus removal efficiency of more than 80%. The percentage of the effluent COD_Cr discharge increased from 10% to 14–17% after installing ozonation and crystallization because of the formation of non-biodegradable organic substances in ozonation process. Energy consumption of the innovative advanced process is comparable or can be even smaller than that of the conventional anaerobic/oxic (A/O) process in spite of the installation of ozonation and crystallization.     

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.     

Catalytic ozonation with non-polar bonded alumina phases for treatment of aqueous dye solutions in a semi-batch reactor

Semi-batch experiments were conducted to investigate the effects of catalyst type, pH, initial dye concentration and production rate of ozone on the catalytic ozonation of the dyes, namely Acid Red-151 (AR-151) and Remazol Brilliant Blue R (RBBR). The used catalysts were alumina, 25% (w/w) perfluorooctyl alumina (PFOA), 50% (w/w) PFOA and 100% (w/w) PFOA. The results showed that the overall percent dye removal after 30 min of the reaction was not affected significantly by the catalyst type. However, highest COD reduction was achieved by ozonation with alumina for AR-151, and 100% PFOA for RBBR at pH 13. The behavior of COD reduction with the increasing amount of perfluorooctanoic (PFO) acid amount can be explained by the enhancement of catalytic activity of PFOA with alkyl chains. For both of the dyes, the highest dye and COD removals were reached at pH 13. The overall dye reduction after 30 min of ozonation was almost independent of the initial dye concentration at relatively low values while at the higher concentrations, it changed with the initial dye concentration for both of the dyes. Similarly, COD reduction changed on a limited scale with the increasing initial dye concentration from 100 mg/L to 200 mg/L; however, an increase of initial dye concentration to 400 mg/L decreased the COD reduction significantly. All the studied production rates of ozone were sufficient to provide almost 100% dye removal in 30 min, whereas the COD removal percentage was increased gradually by the increasing ozone input to the reactor. The reaction kinetics for the ozonation of each dye with and without catalyst was investigated and discussed in the paper.     

Transformation in Bulk and Trace Organics during Ozonation of Wastewater

The aim of this paper is to determine the ozone dosages needed to oxidize bulk and trace organics. Treated effluent from eight full-scale wastewater treatment plants was collected and subjected to lab-scale ozonation. Because both organics and inorganics exert ozone demand, an approach was developed to calculate only the ozone demand associated with organics. This method allowed normalization of dosing parameters to correlate with removal of color, UV absorbance, plus oxidation of trace organics and nitrosamine precursors. We also showed that ozonation effectively reduces the fraction of organic matter characterized as “colloidal organic matter,” thereby reducing the potential for membrane fouling.     

Oxidative Treatment of a Wastewater Stream from a Molasses Processing Using Ozone and Advanced Oxidation Technologies

The discoloration of a biologically pretreated wastewater stream from a molasses processing by ozonation and two advanced oxidation processes (O₃/H₂O₂ and O₃/γ-irradiation, respectively) was studied. Color removal occurred with all three processes with almost the same efficiency. The main difference between the methods applied was reflected by the BOD increase during the discoloration period. By ozonation it was much higher than by AOPs, but it also appeared with AOPs. AOPs therefore, were not appropriate as an effective BOD control during discoloration.     

Toxicity Assay in Kraft E1 Effluent Treated by Ozone: Algae Growth Inhibition and Cytotoxicity in V79 Cells

The efficiency of an ozonation process in the degradation of the Kraft E₁ effluent was evaluated. The investigation was focused on the reduction of chemical oxygen demand, total phenols, color and the absorbance at 254 nm. The chronic toxicity was evaluated by growth inhibition of algae Selenatrum capricornutum and cytotoxicity evaluation of effluents samples by determination of the nucleic acid content (NCA) endpoint. After 60 minutes of ozonation, COD and UV₂₅₄ only reached 21% and 34% efficiency reduction. Total phenols and color were more rapidly removed (at 10 minutes of treatment). The results showed that the chronic toxicity (Selenastrum capricornutum algae) decreases for all effluent doses studied. The cytotoxicity assay indicated that toxic compounds were not generated by the ozonation process.     

Removal of Dissolved Organic Carbon and Color from Dyeing Wastewater by Pre-Ozonation and Subsequent Biological Treatment Using Test-Scale Plant

The effects of pre-ozonation and subsequent biological treatment process on the decrease in dissolved organic carbon (DOC) and color were investigated in a test-scale plant of 5 m³/d capacity using actual raw wastewater (RW) from a dye works. Ozone dosage rate and contacting time were around 70 mg/L on average and 30 min, respectively. The DOC concentration was gradually decreased from 36.1 to 19.3 mg/L on average through the process and the DOC removal rates were 24.4% after ozonation and 46.5% after subsequent biological treatment. The average color value was rapidly decreased from 1.75 to 0.20 after ozonation, and the color removal rate was 88.6%. The values of adsorbable organic halide formation potential (AOXFP) and trihalomethane formation potential (THMFP) were gradually decreased by each treatment process, indicating the increased safety of the treated water. Slight morphological differences due to decomposition of the predominant bacteria by residual ozone were observed. The DOC removal rate brought about by pre-ozonation was slightly higher than that by the process consisted of biological treatment and post-ozonation, although no obvious difference in the color removal was observed between them.     

Optimization and Control of Ozonation Plant Using Raw Water Characterization Method

This study was undertaken to devise an innovative method for optimization and control of ozone dosage in drinking water ozonation treatment plants. The method is based upon a specifically-conceived analytical procedure, which can accurately measure the ozone decomposition rate. This was found to consist of two apparent phases: an instantaneous ozone demand (ID) phase and a relatively slower ozone decay (pseudo first-order rate constant, kc) phase. Those parameters, ID and kc were measured in a demonstration plant by the testing procedure in order to characterize raw water and process water, and utilized an Automatic Ozone Control Unit (ACU) to optimize preozonation (with parameter, ID) and postozonation (with parameter, kc).     

Impact of Ozonation on Decolorization and Mineralization of Azo Dyes: Biodegradability Enhancement,By-Products Formation,Required Energy and Cost

In the present study ozonation process was implemented to analyze the effect of ozonation time on the rate of chemical oxygen demand (COD) removal, mineralization and rate of decolorization of azo dyes. Three types of azo dyes i.e. Acid Red 14, Direct Red 28 and Reactive Black 5 were selected. Decolorization and mineralization of samples were conducted in batch scale. The COD and color removal efficiency were found to be increasing at a certain time of ozonation. The results with Acid Red 14, Congo Red and Reactive Black 5 dyes solutions lead to maximum COD reduction of 75%, 67% & 50% respectively. 93%, 92% and 94% color removal were achieved after 25 min of ozonation time of the same dyes which highlighted that ozonation process was found to be more efficient for reactive dye decolorization. Ozonation by-products analyzed by ion chromatography resulted that it partially mineralized with the formation of chloride, fluoride, sulphate, nitrate and oxalate ions. During ozonation process a rapid decrease in pH value indicated the acidic nature of by-products. The effect of buffered dye solutions on the ozonoation process highlighted that the decolorization efficiency decreases in comparison to unbuffered dye solutions. Ozonation led to enhancement of biodegradability ratio (BOD₅/COD) and increased electrical conductivity of the dye solutions. Optimum ozonation time required for degradation of dye solutions reflected the evaluation of energy consumption and cost of the treatment after ozonation.     

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.     

Combination of Ozonation and the Fenton Processes for Landfill Leachate Treatment: Evaluation of Treatment Efficiency

Single processes such as ozonation, ozone/hydrogen peroxide, Fenton and several combined treatment schemes were applied for leachate collected from a waste disposal site. The implementation of combined Fenton and ozonation processes resulted in the highest chemical oxygen demand removal (77% from initial value) among all the treatment methods applied, while biodegradability improvement was observed during the Fenton pre-treatment only. Some decrease of chemical oxygen demand was obtained during the single ozonation or combined schemes including ozone resulting in slight if any biodegradability improvement. The addition of hydrogen peroxide to ozonation did not enhance chemical oxygen demand, dissolved organic carbon or biochemical oxygen demand removal compared to ozone alone. Ferric chloride coagulation used as a pre-treatment stage did not improve subsequent chemical oxygen demand removal by ozonation or the Fenton processes. Taking into account the effective chemical oxygen demand, dissolved organic carbon removal and biodegradability improvement the single Fenton process seems to be a preferable treatment method for the leachate treatment. Some reduction in toxicity to Daphnia magna was observed after the application of the studied treatment methods.