Influence of Ozone on the Photocatalytic Oxidation of Organic Compounds

Heterogeneous photocatalytic oxidation processes using titanium oxide as a photocatalyst are widely discussed topics in research for water and waste water treatment. Oxygen fed into the systems is normally used as oxidizing agent. However few investigations exist concerning the use of ozone as an additional oxidant. In this work the influence of ozone on the photocatalytic degradation of organic compounds are described. The results are compared with those by using ozone, UV/O₃ and UV/TiO₂/O₂. The oxidation reactions were performed at pH 3 and 7.

In this research compounds of the different classes were used: glyoxal, pyrrole-2-carboxylic acid, p-toluenesulfonic acid and naphthalene-1,5-disulfonic acid. Depending on the classes of compounds in some cases the elimination rates of the initial compounds is enhanced by using UV/TiO₂/O₃ compared to UV/O₃ or O₃ alone. But in all cases greatest DOC elimination is achieved by using UV/TiO₂/O₃.     

Ozonation And AOP Parameter Estimation From Countercurrent Film Absorber Data

Degradation of phenolic compounds in Kohtla-Järve oil shale ash dump wastewater (North-East Estonia) by O₃, O₃/UV, O₃/H₂O₂, O₃/H₂O₂/UV, O₃/TiO₂ and O₃/TiO₂/UV treatment in a countercurrent film absorber was studied experimentally. The mathematical model and the simulation algorithm of the processes were developed. The random search optimizer was applied to evaluate the values of reaction rate constant, mass transfer enhancement factor, stoichiometric coefficient and volatilization coefficient for organics into the process models. The evaluated coefficients for individual phenolic compounds, total content of phenolic compounds and COD for different oxidation systems are presented and discussed. “Operation” of the simulated film absorber (based on the evaluated coefficients) and the experimental column are compared.     

Sequential Partial Ozonation for the Treatment of Wastewater Concentrate: Practical Implications From a Conventional and (Eco) Toxicological Perspective

This article compares multi-stage ozonation-biological treatment processes [O₃ - Biodegradation - O₃ - Biodegradation] and conventional partial ozonation processes [O₃ - Biodegradation] for the removal of S_COD and toxicity from a recalcitrant and toxic wastewater concentrate. Both direct (pH 7.5) and advanced (pH 11.5) ozonation are evaluated. Short-term estimation methods for biodegradability (respirometry) and toxicity (30 min Vibrio fisheri luminescence inhibition) are evaluated for their use in process control.     

Comparison of Different Oxidation Methods for Recalcitrance Removal of Landfill Leachate

In this work several oxidation methods, such as conventional ozonation, O₃/UV, O₃/UV/ferrous iron and Fenton oxidation, for the removal of recalcitrant organic matter present in landfill leachates are evaluated. The samples of the leachate are taken after a biological treatment and membrane ultra-filtration (UF). The contribution of the UV radiation and the effect of ferrous iron ions on the ozone process efficiency is discussed. At lower ozone dosages, the partial oxidation efficiency is reduced as compared to conventional ozonation and therefore, a higher degree of mineralization of the organic matter is achieved. Finally, the best results are obtained by the Fenton oxidation, however, based on economic considerations this method is not recommended.     

Comparison of Ozone and Hydroxyl Radical-Induced Oxidation of Chlorinated Hydrocarbons in Water

The efficiency of ozonation and advanced oxidation processes such as ozone/UV, ozone/H₂O₂ and H₂O₂/UV was assessed for chlorinated hydrocarbons using a closed batch-type system. 1,1-Dichloropropene (DCPE), trichloroethylene (TCE), 1-chloropentane (CPA), and 1,2-dichloroethane (DCA) were used as model compounds.

The direct reaction between substrates and ozone predominated at lower pH, which resulted in the efficient oxidation of the olefin, DCPE. At higher pH, ozonation resulted in more efficient oxidation of the chlorinated alkanes, with a corresponding decrease in the efficiency of DCPE oxidation. Consistent results were observed for ozone/H₂O₂ and ozone/UV treatment. Due to slow UV-induced decomposition of H₂O₂, the process using H₂O₂/UV (254 nm) resulted in very slow oxidation of all four compounds.

The total ozone requirement to achieve a given degree of elimination (to 37% of the original concentration), δ0.37, was used to assess the combined effects of the direct and indirect reactions for different types of waters.     

EVALUATION OF UV/O3 AND UV/H2O2 PROCESSES FOR NONBIODEGRADABLE COMPOUNDS: IMPLICATIONS FOR INTEGRATION WITH BIOLOGICAL PROCESSES FOR EFFLUENT TREATMENT

Poorly biodegradable compounds reduce the efficiency of biological effluent treatment processes. These are often encountered in pharmaceutical and speciality chemical industries. Advanced oxidation technologies (AOT) are appropriate for the conversion of such compounds into biodegradable entities. Tetrahydrofuran, 1,4-dioxane, and pyridine are heterocyclic compounds that are known to be recalcitrant and nonbiodegradable. AOT were investigated for the destruction of these model compounds. Two forms of AOT, UV-O₃ and UV-H₂O₂, were studied. UV-H₂O₂ treatment resulted in higher biodegradability for tetrahydrofuran; UV-O₃ treatment resulted in higher biodegradability for 1,4-dioxane. For pyridine, neither treatment improved biodegradability. For efficient integration of AOT with biological processes for effluent treatment, it is necessary to evaluate the AOT with multiple objectives, such as level of destruction of target compound, level of reduction in COD, and enhancement of biodegradability. Due to the presence of multiple pollutants in real effluents and in AOT, kinetics of oxidation elucidated with single compounds is unlikely to be useful.     

Advanced Oxidation of Textile Wastewaters

Model dyeing and laundering wastewaters produced during two basic technological operations of the textile industry were subjected to treatment by advanced oxidation processes (AOPs). The following agents were used: ozone (O₃), hydrogen peroxide (H₂O₂) and UV radiation. They were applied separately and in all possible combinations: O₃ + UV, O₃ + H₂O₂, UV + H₂O₂, as well as all three at the same time: O₃ + UV + H₂O₂. Effluents before and after the treatment were analyzed according to requirements of the Polish Standards that included pH, color threshold, COD and concentration of anionic and non-ionic surfactants. Ozonation was carried out in a lab-scale bubble column reactor with a centrally located UV burner. The most effective version of AOPs proved to be the simultaneous use of all three agents. In the case of such treatment of dyeing wastewaters nearly complete discoloration and full decomposition of surface-active substances were obtained at 80% reduction of COD. A similar tendency was observed in the case of laundering wastewater, though in that case the results were slightly worse, which may be explained by much higher initial concentrations of the pollutants. Good treatment effects have also been obtained in combined treatment by simultaneous use of hydrogen peroxide and ozone.     

Oil-Refinery Wastewater Treatment Aiming Reuse by Advanced Oxidation Processes (AOPs) Combined with Biological Activated Carbon (BAC)

The treatment of a refinery wastewater by Advanced Oxidation Processes (AOP) coupled with Biological Activated Carbon (BAC) was investigated aiming to generate water for reuse. O₃/UV and H₂O₂/UV processes were employed to oxidize the organic matter and the BAC process to remove residual organic matter from the AOP effluent. AOP promoted oxidation of recalcitrant organic matter as observed by moderate drops on the treated wastewater absorbance (31–79%) and TOC values (10–18%). BAC filters showed to be effective, reaching average efficiencies of 65% in a sufficiently long period of operation (84 days), while GAC filters were saturated after 28 days. Effluent TOC values in the range of 4 to 8.5 mg/L were achieved by the combined treatment (H₂O₂/UV + BAC), allowing water reuse.     

Advanced Oxidation Processes for the Elimination of Drugs Resisting Biological Membrane Treatment

The recalcitrant pharmaceutical compounds carbamazepine, clofibric acid, diazepam, and diclofenac were monitored in municipal wastewater by ESI-LC-MS and -MS-MS in positive and negative mode. Although biological treatment by conventional and membrane bioreactor failed, the advanced oxidation methods using ozone (O₃), O₃/UV or hydrogen peroxide in combination with UV (H₂O₂/UV), successfully achieved their complete elimination. Target compounds could be confirmed as permanently present pollutants in Aachen-Soers wastewater in concentrations between 0.006 and 1.9 μg L^?1 prior to AOP treatment resulting in a complete elimination.     

Comparison of Different Advanced Oxidation Processes Involving Ozone to Eliminate Atrazine

The oxidation of the herbicide atrazine by advanced oxidation processes (AOP) has been studied. The experiments were carried out in a tubular photoreactor, 2.5 L capacity, capable of providing good contact between the liquid and gas reactants. The decomposition rate of atrazine was determined at different pH using UV radiation, Hydrogen Peroxide, Ozone, Ozone/UV, Ozone/H₂O₂, H₂O₂/UV and Ozone/H₂O₂/UV processes. The effect of three different pH values was studied (4.7, 6.8, 11.7).     

Treatability Study on Membrane Concentrate Containing Pesticides Using Advanced Oxidation Processes

This treatability study evaluated the overall effectiveness of advanced oxidation processes (AOPs) to treat membrane concentrates containing the pesticides bromoxynil and trifluralin. The results of study indicate that high levels of pesticide degradation were achieved using ozone (O₃) plus hydrogen peroxide (H₂O₂) for all concentrate matrices. However, the toxicity of the samples during the O₃/H₂O₂ process was higher than that obtained during ultraviolet (UV) light combined with H₂O₂. Low levels of pesticide oxidation were observed in experiments using a mixture of pesticides during all treatment options.     

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.     

Oxidation of Propylene Glycol Methyl Ether Acetate Using Ozone-Based Advanced Oxidation Processes

The present study investigates the degradation of PGMEA and its TOC removal using O₃, UV/O₃, O₃/H₂O₂, and UV/H₂O₂ processes under various experimental conditions. Ozonation of PGMEA was substantially enhanced in the presence of UV light and H₂O₂. Approximately 33% of TOC enhancement was noted in UV/O₃ process over ozonation process. A linear relationship between PGMEA and H₂O₂ decomposition was observed in O₃/H₂O₂ and UV/H₂O₂ processes. The influence of solution pH on the decomposition of PGMEA was investigated and found that basic medium was the most efficient in all AOPs. After 60 minutes 62.4%, 100%, 90% and 54% of PGMEA decomposition at pH 10.0 was observed in O₃, UV/O₃, O₃/H₂O₂, and UV/H₂O₂ processes, respectively. It is concluded that UV/O₃ process is a promising approach for the oxidation and removal of PGMEA.     

Treatability of Organic Constituents in the Paşaköy Wastewater Treatment Plant Effluent by O3 and O3/H2O2

Effluent from the Pa?aköy Wastewater Treatment Plant was oxidized by using O₃ and O₃/H₂O₂. DOC, COD, UV₂₅₄, total coliform, dissolved ozone and some endocrine disrupting compounds were monitored during oxidation. Results showed that O₃ provided superior disinfection, however, lower reductions in DOC, COD and endocrine disrupting compounds were exhibited compared to O₃/H₂O_2. The highest removal efficiency of DOC, COD and endocrine disrupting compounds were achieved at 0.5 molar ratio of O₃/H₂O_2. The benefit of H₂O₂ addition for advanced oxidation reduced significantly when the mole ratio was increased to 2. Therefore, the mole ratio of H₂O₂ to O₃ is a critical parameter for the design of wastewater oxidation by O₃/H₂O₂.     

Ozone Treatment of Tannery Wastewater Monitored by Conventional and Substance Specific Wastewater Analyses

Ozone is an unstable and highly reactive gas applied in drinking water or wastewater treatment to oxidize and/or mineralize pollutants. Its application in wastewater treatment leads to a destruction of persistent pollutants combined with an improvement of biodegradability. The oxidation of organic and inorganic compounds in tannery wastewater at different pHs applying O₃ was studied. Results after O₃-treatment were determined by conventional wastewater parameters, e.g., total organic carbon (TOC), biochemical oxygen demand after 5 days (BOD₅), and chemical oxygen demand (COD), as well as by substance-specific mass spectrometric analytical techniques, i.e., gas chromatography—mass spectrometry (GC/MS) and liquid chromatography—mass and tandem mass spectrometry (LC/MS and—MSⁿ). In parallel, variations in the toxicity of the tannery wastewater against water organisms before and after O₃-treatment were determined by means of biotoxicity testing, i.e., Daphnia magna Straus and Vibrio fischeri bioassays.     

Optimization of High-Strength Semiconductor Wastewater by Sequential Fenton Oxidation and Gas-Induced Ozonation

Treatment of organic-containing wastewater from a semiconductor plant treated by chemical oxidation was experimentally investigated. The wastewater was characterized by strong color, high chemical oxygen demand (COD) and low biodegradability. Treatment of this wastewater by traditional activated sludge method was essentially impossible. In the present work, advanced chemical oxidations by Fenton’s reagent and ozonation were utilized to tackle the problems of wastewater color and low biodegradability. To facilitate the particulate removal after Fenton oxidation, chemical coagulation using polyaluminum chloride and polymer was adopted as an integral part of the Fenton process. Experimental tests were conducted to determine the effectiveness and the optimum operating conditions of the chemical oxidation methods. Test results demonstrate that the two advanced oxidations were able to lower the wastewater COD concentration from as high as 15,000 mg/L to below 150 mg/L and completely eliminating the wastewater color, resulting in very good quality of the treated wastewater. A generalized kinetic model was employed to describe and elucidate the oxidation mechanisms of oxidation processes and the kinetic parameters of the models were appropriately identified using the test data.     

Photo Assisted Fenton in a Batch and a Membrane Reactor for Degradation of Drugs in Water

Abstract

Some advanced oxidation processes (AOP's) such as Fenton H₂O₂/Fe²⁺, photo assisted Fenton UV/H₂O₂/Fe²⁺, UV photolysis, and photo assisted Fenton—like UV/O₂/Fe²⁺ have been tested for the degradation of Gemfibrozil in aqueous solution in a batch system and then in a membrane reactor. A nanofiltration/reverse osmosis type cross‐linked polyamide, UTC‐60 (Toray) membrane (19 cm²) was used. In the batch degradation tests, the gemfibrozil, used at 5 mg/L, was degraded by employing the four AOP's but numerous peaks of intermediates were observed at the HPLC. Indeed DOC analyses showed poor mineralization in the case of photolysis (3.1%) and UV/O₂/Fe (10%), while it was 62% using the photo assisted Fenton and 24% using the Fenton. Thus in the membrane reactor only the Fenton and the photo assisted Fenton were tested. Obtained results showed a drug degradation higher than 92%, a mineralization higher than 55%, and a membrane retention of the catalyst in solution higher than 95%.     

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.     

Advanced Oxidation Processes Against Phenolic Compounds In Wastewater Treatment

Experimental research into the oxidative treatment of aqueous solutions and wastewaters containing phenolic compounds was undertaken. Ozone, supported by short wavelength UV-irradiation, hydrogen peroxide and titanium dioxide catalyst, was selected as an oxidant in the following combinations: O₃, O₃/H₂O₂, O₃/UV, O₃/TiO₂, O₃/UV/H₂O₂ and O₃/UV/TiO₂. 5-Methylresorcinol was chosen as a model compound for the experiments with synthetic phenolic solutions. The results obtained from these experiments were compared with the results of oxidative purification of wastewaters produced from the thermal treatment of oil shale in Estonia.     

Application of Response Surface Methodology for Coffee Effluent Treatment by Ozone and Combined Ozone/UV

This paper reports a study using ozone (O₃) and combined ozone/ultraviolet (O₃/UV) processes for color removal and caffeine degradation from synthetic coffee wastewater using a second-order response surface methodology (RSM) with a three-level central composite face-centered (CCF) design. The effects of O₃ concentration, initial pH, and reaction time were examined for both processes. The reaction time and pH were statistically significant for caffeine degradation and color removal. In the ozonation process, higher caffeine degradation and color removal were observed in alkaline pH, indicating that ozone attacks indirectly, consequently generating hydroxyl radicals. Regarding the ozone/UV process, it was observed that lower caffeine degradation and color removal occurred at neutral pH, indicating an adverse effect due to lower ozone dissolution and consequently the production of a smaller amount of free hydroxyl radicals. The achieved results showed that the techniques were efficient for color removal (85% and 99%, respectively) and caffeine degradation (88% and 98%, respectively).