Effect of Ozone in UF-Membrane Flux and Dissolved Organic Matter of Secondary Effluent

The focus of this work was to determine the effect of ozone on the removal of dissolved organic matter (DOM) from a secondary effluent and its relation with the permeated flux behavior in an ultrafiltration membrane. To assess the ozone action, the DOM of the secondary effluent was fractionated into its hydrophobic, transphilic and hydrophilic fractions, using XAD-8 and XAD-4 resins. Ozone increased the hydrophilic fraction from 32% to 42%, and this percentage remained unchanged after ultrafiltration of the secondary effluent. Permeate flux dropped to 52% in the first hour of membrane operation, but when ozone was applied as a pretreatment, it could be maintained at 84% within the first hour.     

Ozone-Based Processes Applied to Municipal Secondary Effluents

This study analyzes the performances of 2 methods of oxidation based on ozone, namely ozonation and ozone combined with hydrogen peroxide (O₃/H₂O₂), on two biotreated municipal wastewater effluents. The main parameters monitored to evaluate the effectiveness of the processes were Chemical Oxygen Demand (COD), Dissolved Organic Carbon (DOC) and Biochemical Oxygen Demand (BOD₅). Ozonation and O₃/H₂O₂ treatment removed 44% and 48%, respectively, of the COD, after 90 min, of the secondary effluent of Calafell wastewater treatment plant (Spain). On the secondary effluent from the Grasse wastewater treatment plant (France), these same treatments (O₃; O₃/H₂O₂) achieved, respectively, a degradation of 52% and 100% of the COD after 60 min. The transferred ozone dose (TOD) during Calafell and Grasse effluents' ozonation were 122 mg·L^?1 and 77 mg·L^?1 after 90 min, respectively. A low removal of DOC was monitored during both O₃ or O₃/H₂O₂ treatments applied to Calafell wastewater, respectively 12% and 14%. Better DOC reductions were obtained on the water of Grasse treated with O₃ or O₃/H₂O₂, respectively, 48% and 60%. In addition, ammonia nitrogen was oxidized to nitrate nitrogen thus giving rise to an over ozone consumption. And finally, both processes proceeded with an increase of pH values. These results highlight the strong dependency of O₃ or O₃/H₂O₂ treatment effectiveness in terms of dissolved organic matter (DOM) removal and ozone consumption on wastewater composition (organic and inorganic substances).     

Chlorine reactivity and transformation of effluent dissolved organic fractions during chlorination

The trihalomethane formation potential (THMFP) and structural characteristics of dissolved organic matter (DOM) in the secondary effluent from the Wenchang Wastewater Treatment Plant (Harbin, China) were studied and the alterations in structural and chemical compositions of the DOM during chlorination were evaluated. Using XAD-8 and XAD-4 resins, DOM was fractionated into 5 fractions: hydrophobic acid (HPO-A), hydrophobic neutral (HPO-N), transphilic acid (TPI-A), transphilic neutral (TPI-N) and hydrophilic fraction (HPI). Results showed that HPO-A and HPI dominated in the secondary effluent, collectively accounting for more than 66% of the DOM as dissolved organic carbon, and 70-84% of the THMFP of DOM was converted from the reaction of chlorine with HPO-A and HPI. Fourier-transform infrared (FT-IR) analysis illustrated that the functional groups involved in the chlorination reaction were aromatic C=C, C-O, C=O, C-Cl and amide functional groups. Proton nuclear magnetic resonance (¹H NMR) analysis indicated that HPO-A, HPO-N, TPI-A and TPI-N had significantly decreased aromatic protons (H_Ar) after chlorination. Although HPO-A, HPO-N, TPI-A and TPI-N exhibited different fluorescence changes during chlorination, the wavelength that corresponded to the position of the normalized emission band at its half-intensity (λ_0.5) for the four fractions decreased as a result of chlorination.     

Effects Of Ozone On Kraft Process Pulp Mill Effluent

Effluent from a kraft process pulp mill was studied in a batch reactor for ozone doses between 50 and 200 mg O₃/L to identify the relative suitability of ozone application locations in the treatment process and see the improvements in biotreatability of wastewaters from a kraft process pulp mill. Laboratory acclimatized seed were used for BOD tests for ozonated and unozonated samples. The inhibitory effects were minimized by using optimum dilutions. The studies were divided into three major sections: characterization of mill effluent; ozone system calibration, and reactor design; and ozonation of mill effluent. Seed for Biochemical Oxygen Demand tests were acclimatized in batch units for primary, bleach and secondary effluents separately. The inhibitory effects which were noted with unacclimatized seed, were reduced by using laboratory acclimatized seed and optimum dilution which were determined during the characterization phase.

The batch reactor designed for the studies consisted of a cylindrical section for holding effluent, and a top spherical section for ozone/oxygen mixture. The reactor proved to be effective for controlling ozone dose. The variation in the applied ozone dose was less than 5 mg/L.

Bleach and primary effluents were treated with 50 and 100 mg/L ozone doses. Duplicate experiments were conducted for these effluents. Secondary effluent was studied for 50,100,150 and 200 mg/L ozone doses. Six replicate experiments were conducted for 50 and 100 mg/L ozone doses, whereas two experiments were carried out for 150 mg/L and one experiment for 200 mg/L ozone dose.

The results were analyzed using 't' test for paired experiments and ANOVA table for statistical confirmation. Residuals were plotted to check the assumptions of constant variance and normal distribution. The results indicated that 50 and 100 mg O₃/L effectively removed color from bleach effluent and primary effluent, but did not significantly change the BOD. Ozone was found to be effective for secondary effluent, as BOD₅ was increased by 65% for 50 and 100% for 100 mg O₃/L doses. The corresponding reduction in color was 62% and 82%, respectively. K_e and L_o values for the BOD equation were calculated by using the non-linear least square method for the BOD equation, giving joint confidence regions for the calculated parameters. It was concluded that ozone is most effective for the removal of color and the increase of BOD in secondary effluent.     

Examining the Role of Effluent Organic Matter Components on the Decomposition of Ozone and Formation of Hydroxyl Radicals in Wastewater

The impact of wastewater derived effluent organic matter (EfOM) on the decomposition of ozone and formation of hydroxyl radicals (HO^●) was evaluated for four wastewaters (sites A, B, C1 and C2). The reactivity of EfOM was assessed by fractionation into four apparent molecular weight (AMW) fractions (<10 kDa, <5 kDa, <3 kDa, and <1 kDa). The R_CT, defined as the ratio of HO^● exposure to ozone exposure (∫HO^●dt?/?∫O₃dt), was measured for all fractions and bulk waters (at times greater than 5 seconds), with an initial ozone dose equal to the total carbon concentration of EfOM (ozone:DOC ratio of 1). The R_CT of all the samples and ozone first-order decay rates of two of the waters increased significantly (95% confidence) from the bulk sample to the <10 kDa fraction, and decreased with AMW. This indicates that the intrinsic capacity of different molecular weight fractions of the EfOM have different reactivity with ozone.     

Effect of Ozone on Removal of Dissolved Organic Matter and its Biodegradability and Adsorbability in Biotreated Textile Effluents

A study was conducted on the efficacy of ozonation in removing dissolved organic matter (DOM) in biotreated textile effluents and effects on its biodegradability and adsorbability. Results showed the efficient removal of color and fluorescence compounds were achieved through ozonation, due to increasing hydrophilicity and lowering molecular weight of DOM. A significant biodegradability improvement was also observed, and DOM adsorbability on activated carbon was highly dependent on ozone dosage. As the key parameter, consumed 3.8 g O₃/?g TOC₀ was the optimal dosage in the hybrid process combining ozonation with biological activated carbon (BAC) for wastewater reclamation.     

Oxidation of Aged Raw Landfill Leachate with O3 Only and O3/H2O2: Treatment Efficiency and Molecular Size Distribution Analysis

An aged raw landfill leachate was taken from the equalization storage tank at Clover Bar Landfill Leachate Treatment Plant, Edmonton, Alberta, Canada. The average quality parameters of this leachate were: COD=1,090mg/L, BOD₅=39mg/L, color=1,130 TCU, NH₃-N=455mgN/L, alkalinity=4,030mg/L as CaCO₃and pH=8.30. The major fraction of this leachate was large refractory organic compounds. Ozone (O₃) only and O₃ combined with hydrogen peroxide (O₃/H₂O₂) were applied to treat this leachate, aiming at enhancing COD and color reduction and increasing its biodegradability (i.e., the ratio of BOD₅/COD). All of the O₃ only and O₃/H₂O₂ oxidation experiments were performed in a gas washing bottle equipped with a fine bubble diffuser. The used ozone dose ranged from 1.2 to 12.5g O₃/L leachate for O₃ only treatment, and 1.8 to 13.8g O₃/L leachate for O₃/H₂O₂ treatment. H₂O₂ dose for O₃/H₂O₂ treatment was 0.63g H₂O₂/L leachate. COD, BOD₅, color, NH₃-N, nitrite+nitrate, and alkalinity were measured before and after treatment. Meanwhile the molecular size distribution of the leachate, before and after treatment, was analyzed by using a high-performance liquid chromatograph (HPLC) with gel filtration column and UV detector at 254nm. The addition of H₂O₂ had an insignificant effect (at 5% significance level) on enhancing COD and color reduction. After oxidation, the maximum BOD₅ increase was about 110% for O₃/H₂O₂ treatment and about 141% for O₃ only treatment at a used ozone dose of 3.6g O₃/L leachate and 2.6g O₃/L leachate for O₃/H₂O₂ and O₃ only, respectively. As the used ozone dose increased, NH₃-N and alkalinity decreased considerably, and nitrite+nitrate increased accordingly. Treatment efficiency models, which describe the changes in COD, BOD₅/COD, NH₃-N, nitrite+nitrate, and alkalinity as functions of the used ozone dose, were developed. Statistically (at 5% significance level), the treatment efficiency models for both treatments are not different. According to the results of molecular size distribution analysis, no correlation was observed between the BOD₅ increase and oxidation by-products’ formation.     

Enhancing Agro-Industrial Wastewaters Depuration by Ozone Oxidation

This article explores the application of several ozone-based technologies on the abatement of a bio-refractory stream coming from an elderberry juice plant (BOD₅/COD = 0.26). The impact of ozone inlet concentration and pH was addressed firstly, followed by the analysis of the O₃+H₂O₂ combined system. Finally, the activity and stability of two solid catalysts (Mn-Ce-O and Fe-Mn-O) was assessed. None of the approaches produced values within the legal thresholds for direct discharge into water-courses. It is advisable to integrate the chemical treatment with a bio-reactor. Thus, single ozonation at pH = 3 (BOD₅/COD = 0.48), O₃+[H₂O₂] = 32.5 mM (BOD₅/COD = 0.46) and O₃+Mn-Ce-O at pH = 3 (BOD₅/COD = 0.44) are promising strategies.     

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.     

An Insight into Dissolved Organic Matter Removal Characteristics of Recycling Filter Backwash Water: A Comparative Study

It is necessary to put all aspects,,namely raw water characteristics, corresponding FBWW, and coagulation mechanisms, i.e., charge neutralization and sweep flocculation together to make clear the dissolved organic matter (DOM) removal characteristics and the fate of fractionations in recycle design. The DOM characteristics of molecular weight (MW) distribution, hydrophobicity, and fluorescence in source water W1 (synthesized water) and W2 (“Longtan” lake water), FBWW and treated water samples therefore are identified, and three recycling ratios of 2%, 5%, and 8% as compared to control (0%) are conducted. It is found that DOM within FBWW becomes more hydrophilic and lower MW as compared to corresponding source water. Recycling trials indicate that higher DOM concentrations and more low-MW fractions are not of any benefit to enhance UV₂₅₄ and DOC removal. Hydrophobic acid can be further eliminated in case recycling particles mainly produced by sweep flocculation, while weakly hydrophobic acid and hydrophilic fraction can be enhanced and removed under recycling particles mainly formed by charge neutralization. Higher molecular weight fraction (>30 kDa) exhibits potentially enhanced removal at preferred recycling ratio of 5%. Fluorescent characteristics analysis demonstrate that recycling FBWW can effectively improve humic-like substances removal, but the protein-like matters are resistant to be eliminated with unvaried structure.     

Evaluation of Process Control Alternatives for the Inactivation of Escherichia coli,MS2 Bacteriophage,and Bacillus subtilis Spores during Wastewater Ozonation

Dissolved ozone concentration integrated over time (CT) is a reliable indicator of disinfection efficacy in drinking water treatment. However, ozone CT may not be measurable in some wastewater ozone applications. In this study, alternative process control parameters, specifically ozone to total organic carbon (O₃:TOC) ratio, differential UV₂₅₄ absorbance (ΔUV₂₅₄), and differential total fluorescence (ΔTF), were correlated with the inactivation of Escherichia coli, the bacteriophage MS2, and Bacillus subtilis spores in five secondary wastewater effluents. CT values greater than 9 mg-min/L were generally required for measurable inactivation of B. subtilis spores, and CT values of 1 and 2 mg-min/L consistently achieved greater than 6- and 5-log inactivation of MS2 and E. coli, respectively. The O₃:TOC, ΔUV_254, and ΔTF correlations for MS2 and B. subtilis were useful for predicting inactivation, while those of E. coli were characterized by greater variability. [Supplementary materials are available for this article. Go to the publisher's online edition of Ozone: Science & Engineering for the following free supplemental resources: additional figures and data tables.]     

Toxicity and Biodegradability Behavior of Xenobiotic Chemicals Before and After Ozonation: A Case Study with Commercial Textile Tannins

Ozonation of a natural tannin (NT; COD_o?=?1195 mg/L; TOC_o?=?342 mg/L; BOD_5,o?=?86 mg/L) and a synthetic tannin ST; COD_o?=?465 mg/L; TOC_o?=?55 mg/L; BOD_5,o?=?6 mg/L) being frequently applied in the polyamide dyeing process was investigated. Synthetic wastewater samples containing these tannins individually were prepared and subjected to ozonation at varying ozone doses (625– 1250 mgO₃/L wastewater), at pH?=?3.5 (the application pH of tannins) and pH?=?7.0 at an ozone dose of 1125 mgO₃/L wastewater. The collective environmental parameters COD, TOC, BOD₅, UV₂₅₄ and UV₂₈₀ (UV absorbance at 254 nm and 280 nm, representing aromatic and unsaturated moieties, respectively) were followed during ozonation. Changes in the biodegradability of the tannins were evaluated in terms of BOD₅ measurements conducted before and after ozonation. In addition, activated sludge inhibition tests employing heterotrophic biomass were run to elucidate the inhibitory effect of raw and ozonated textile tannins towards activated sludge biomass. Partial oxidation (45% COD removal at an ozone dose of 750 mg O₃/L wastewater and pH?=?3.5) of ST was sufficient to achieve elimination of its inhibitory effect towards heterotrophic biomass and acceptable biodegradability improvement, whereas the inhibitory effect and biodegradability of NT could not be reduced via ozonation under the same reaction conditions.     

Changes in the Chemical Nature of a Biologically Treated Wastewater During Disinfection by Ozone

Pilot plant studies were carried out on the effect of ozone on the chemical content of a secondary domestic and industrial sewage. Results are expressed in terms of COD, BOD₅, nitrite ion concentrations, bacterial counts, XAD-4-extraetable compounds, and free amino acid concentrations. Ozone dosages of 6 to 12 mg/L were found to reduce levels of fecal bacteria, COD and nitrite ion concentrations significantly, to modify the nature and the concentration of XAD-4-extraetable compounds, and to increase the concentration of free amino acids.     

Fate of Cr(III) during Ozonation of Secondary Municipal Wastewater Effluent

ABSTRACT

In the present study, the fate of trivalent chromium (Cr(III)) during ozonation of ultrapurified water and wastewater effluent was investigated. In experiments conducted in phosphate buffered ultrapurified water, O₃ alone in excess was inefficient to oxidize Cr(III) (only about 10–15% of total Cr(III) content), while in presence of the secondary oxidant, OH radical, almost all Cr(III) was oxidized to hexavalent chromium (Cr(VI)). In a wastewater effluent, spiked with Cr(III), only about 10–20% of Cr(III) was oxidized with specific ozone doses in the range 0.15–1.5 gO₃/gDOC, although O₃ and OH radical were both available for reaction. Cr(VI) formation was monitored in parallel with the abatement of some common micropollutants, reacting with differing apparent second-order rate constants with ozone, decreasing in the order carbamazepine>> benzotriazole> atrazine> p-chlorobenzoic acid (pCBA). Carbamazepine and benzotriazole were abated to >80% for specific O₃ doses of 0.3 gO₃/gDOC and 0.8 gO₃/gDOC, respectively. The more ozone-resistant compounds (atrazine and pCBA) required a specific ozone dose of about 1.25 gO₃/gDOC for the same relative abatement. At this specific ozone dose (i.e., 1.25 gO₃/gDOC), only about 20% of Cr(III) was oxidized to Cr(VI), whereas only 10% of Cr(III) was oxidized to Cr(VI) at a more realistic specific ozone dose for enhanced wastewater treatment for micropollutant abatement (0.5 gO₃/gDOC). Therefore, for typical Cr(III) levels in municipal wastewaters, effluent ozonation only leads to toxicologically insignificant Cr(VI) concentrations.     

Post-Treatment of Pulp and Paper Industry Wastewater by Advanced Oxidation Processes

The aim of this study was to investigate the effectiveness of chemical oxidation by applying ozonation, combination of ozone and hydrogen peroxide and Fenton's processes for decolorization and residual chemical oxygen demand (COD) removal of biologically pretreated pulp and paper industry effluents. The batch tests were performed to determine the optimum operating conditions including pH, O₃, H₂O_2, and Fe²⁺ dosages. H₂O₂ addition reduced the reaction times for the same ozone dosages; however combinations of ozone/hydrogen peroxide were only faintly more effective than ozone alone for COD and color removals. In the Fenton‘s oxidation studies, the removal efficiencies of COD, color and ultraviolet absorbance at 254 nm (UV₂₅₄) for biologically treated pulp and paper industry effluents were found to be about 83, 95, and 89%, respectively. Experimental studies indicated that Fenton oxidation was a more effective process for the reduction of COD, color, and UV₂₅₄when compared to ozonation and ozone/hydrogen peroxide combination. Fenton oxidation was found to have less operating cost for color removal from wastewater per cubic meter than the cost for ozone and ozone/hydrogen peroxide applications.     

Effects of O3, O3/H2O2 and Coagulation on Natural Organic Matter and Arsenic Removal from Typical Northern Serbia Source Water

The objectives of this study were to investigate the effects of ozone and the O₃/H₂O₂ process on FeCl₃ coagulation efficiency for the removal of the high content of natural organic matter (NOM) and arsenic (As) from groundwater (DOC = 9.27 ± 0.92 mg/L; 51.7 ± 16.4 µg As/L). Arsenic and NOM removal mechanisms during coagulation/flocculation are well investigated. However, data concerning arsenic removal in the presence of NOM, which is the subject of this article, are still insufficient. Laboratory and pilot plant test results have shown that the competition of NOM and As for adsorption sites on the coagulant surface have great influence on coagulation/flocculation efficiency for their removal. With both oxidation pre-treatments, arsenic content after the coagulation process was less than 2.0 µg/L in treated water. Application of ozone has a lower influence on coagulation efficacy in terms of DOC reduction, compared to the O₃/H₂O₂ process with the same ozone dose.     

Oxidation of Emerging Contaminants during Pilot-Scale Ozonation of Secondary Treated Municipal Effluent

The transformation of 41 target emerging contaminants in secondary treated municipal wastewater effluent in Canada was examined at pilot-scale, at transferred ozone doses of 2.8 mg/L (0.46 O₃/mg DOC) and 4.4 mg/L (0.72 mg O₃/mg DOC). In general, transformation efficiencies of CECs either increased or were retained at the higher ozone dose. The higher ozone dose of 0.72 mg O₃/mg DOC (Z_spec = 0.6 mg O₃/mg DOC) was sufficient to transform 21 of the 31 detected CECs by over 80% as well as achieving the disinfection target of < 200 MPN E. coli per 100 mL.     

Interaction of ozone and organic matter in coagulation with inorganic polymer flocculant-PACl: Role of organic components

In this study, two model waters were used to evaluate the ozone effect on aquatic organic matter (AOM) removal by coagulation with inorganic polymer flocculant (IPF)-polyaluminum chloride (PACl). Flocs formation during coagulation processes were detected by using PDA (Photometric Dispersion Analyzer). Apparent molecular weight distribution (AMWD) and resin fractionation (RF) were also performed to characterize the change of AOM as a result of pre-ozonation. The experimental results show that the dosage of O₃, characteristics and composition of AOM are the most important factors on the behavior of coagulation. Great differences have been found between the two model waters. Coagulation in model water 1 (MW1) (composed of humic acids) is impaired markedly by pre-ozonation, as more DOC (Dissolved Organic Carbon) is produced with increasing O₃ dosage. Floc formation, as exhibited from decreasing of the slopes of FI (Flocculation Index), is retarded gradually during coagulation process. Although residual turbidity is reduced with 1.15 mg/L O₃, removals of DOC and UV₂₅₄ all decreased. As for model water 2 (MW2) (composed of salicylic acid), FI is retarded also, but turbidity and DOC removals of coagulation after pre-ozonation are improved to a certain extent. Coagulation performance judged from removal of DOC is improved distinctly by pre-ozonation. Fractionation results show that molecular weight of organic matter (OM) of MW1 is converted from higher to lower; and OM becomes from more hydrophobic to more hydrophilic, which might be one of the mechanisms involved in the impairment of ozonation on coagulation effect. OM in MW2 is oxidized and mineralized to a greater extent, thus its impairment on coagulation is released. Finally, according to water properties, some proposed applications were provided for application of ozone in water treatment process.     

Hydroxyl Radical/Ozone Ratios During Ozonation Processes. II. The Effect of Temperature,pH, Alkalinity,and DOM Properties

The influence of temperature, pH, alkalinity, and type and concentration of the dissolved organic matter (DOM) on the rate of ozone (O₃) decomposition, O₃-exposure, ?OH-exposure and the ratio R_ct of the concentrations of ?OH and O₃ has been studied. For a standardized single ozone dose of 1 mg/L in all experiments, considerable variations in O₃-exposure and ?OH-exposure were found. This has important implications for water treatment plants regarding the efficiency of oxidation and disinfection by O₃. In oligotrophic surface waters and groundwaters, minimal calibration experiments are needed to model and control the ozonation process, whereas in eutrophic surface waters more frequent measurements of O₃ kinetics and R_ct values are required to evaluate seasonal variations.     

Ozonation of complex industrial park wastewater: effects on the change of wastewater characteristics

BACKGROUND: Ozonation of complex industrial park wastewater was carried out in a semi‐batch reactor. The variation of wastewater characteristics was evaluated based on the analysis of 5‐day biochemical oxygen demand (BOD₅) concentration, BOD₅/chemical oxygen demand (COD) ratio, COD fractionation, and dissolved organic carbon (DOC) molecular size distribution before and after ozonation. RESULTS: The experimental results indicated that low efficiency of COD removal with increasing tendency of BOD₅ concentration generally appeared after ozonation. Also, the BOD₅/COD ratio increased from an initial of 0.27 to a maximum of 0.38. The COD fractionation tests revealed that most of the inert soluble COD was transformed to biodegradable soluble COD at 30 min of reaction time. Additionally, the DOC molecular size distribution tests showed that the fraction larger than 500 kDa was significantly decreased and the fraction smaller than 2 kDa was increased when the reaction time was prolonged to 240 min. CONCLUSION: This study verified that partial oxidation of the complex industrial park wastewater by ozonation could enhance wastewater biodegradability. The biodegradability enhancement was primarily because the inert soluble COD fraction was converted to the biodegradable soluble COD and the high molecular weight fraction of DOC was shifted toward the low molecular weight fraction. Copyright © 2009 Society of Chemical Industry