A Review on the Applications of Ozonation for the Treatment of Real Agro-Industrial Wastewaters

Regarding agro-wastewaters, the strong loads in bio-refractory substances and seasonality reduce the efficiency of biological treatments and ozonation can play an important role, so that this article reviews its application for such streams. Indeed, biodegradability and toxicity removal was assessed for a wide range of agro-effluents such as olive mill, wineries and distilleries, pulp and paper, cork and cheese production. Solid catalysts reveal promising potential, even though literature is still scarce reporting their use to actual streams. Thus, forthcoming research must embrace catalytic ozonation and continuous pilot-scale reactors behavior on the depuration of real agro-wastewaters to ensure future industrial application.     

Biodergradability and GAC Adsorbability of Micropollutants by Preozonation

In order to evaluate the effect of preozonation on GAC adsorbability and biodegradability and to discuss the performance of BAC, three kinds of batch experiments have been conducted, using humic acid as the test substance. Conclusively, it is recognized that preozonation evidently improves the biodegradability of humic acid, but the equilibrium adsorption constant k, is not changed. However, the adsorption rate is greatly improved. Based on these results and continuous experiments, the characteristics of the removal mechanism of organics by a BAC filter and a GAC filter are compared.     

The Effect of Ozonation on the Removal of Organics by Coagulation – Flocculation

We present here some works which take place in the particular framework of the study of drinking water treatment of reservoir waters which contain high concentrations of organics, mainly humic substances. Previous studies on coagulation of fulvic acid solutions have proved that the optimal removal of organic matter was reached at acidic pH with 2 mg of ferricion per mg or organic carbon (summarized in this paper). The main question in this study is to know what is the impact of preozonation on the removal of organics by iron (III) coagulation.

The study of the behavior of organics, in terms of UV-absorbance and TOC measurements was made on three aquatic fulvic acids and on two raw waters. The experiments carried out with fulvic acids showed that preozonation (at 0.5 mg O₃/mg C) of fulvic acid appeared to have shifted the region of the optimal DOC removal towards the higher coagulant dose. Furthermore, increasing ozone doses led to a slight decreasing of coagulation efficiency at constant coagulant dose. With two raw waters, preozonation at low ozone doses (0.2 mg 0₃/mg C) was found to improve very slightly the elimination of organic matter, while high ozone doses (0.9 mg O₃/mg C) led to a disturbance of TOC elimination by iron coagulation.     

Application of Individual and Simultaneous Ozonation and Adsorption Processes in Batch and Fixed-Bed Reactors for Phenol Removal

Ozonation, adsorption onto activated carbon and catalytic ozonation in batch and in a fixed-bed reactor for the removal/degradation of phenol and COD were investigated. In the case of batch ozonation the oxidation capacity was greater than 6.9 g of phenol/g O₃, while the continuous ozonation system degraded 40% of the phenol and reduced the COD by 27.9%. The adsorption process provided over 99% removal for phenol and COD; however, it treated only 5 L compared with 17 L for the combined process, which also increased the total area and pore volume of the activated carbon, due to the formation of pores and a widening of micropores.     

Intrinsic Activity of SBA-like Silica in the Catalytic Ozonation of Organic Pollutants

Hydrothermal synthesis using two gel compositions: i. 1 SiO₂: 0.059 P123: 56.130 HCl: 607.638 H₂O; ii. 1 SiO₂: 0.006 P123: 0.013 F127: 42.439 HCl: 442.876 H₂O, resulted in highly crystalline SBA-15 and SBA-16 like silica with intrinsic activity in the catalytic ozonation of oxalic acid (OA), phenol (φ-OH) and Orange G (OG) in water at room temperature. X-ray diffraction, nitrogen adsorption–desorption, transmission and scanning electron microscopies revealed highly ordered mesoporous structure, with large surface area, regular channels and uniform particle size. UV-Vis analysis provided faster, more precise and reliable assessments of the decomposition yield and process selectivity than the conventional and laborious method of Chemical Oxygen Demand (COD). The ozone reactivity was found to be favored by increasing size of the organic substrate. OG and phenol decomposition required shorter ozonation time (20, 15 min, respectively) than OA, involving mainly phenyl ring hydroxylation and cleavage. Measurements through thermal programmed desorption of carbon dioxide and water revealed that the catalytic activity of the SBA samples involves adsorption via both acid-base and hydrophobic interactions. Suitable SBA modifications allow tailoring these interactions for even faster ozonation without persistent traces of short chain derivatives.     

Ozonation of Several Organic Compounds Having Low Molecular Weight under Ultraviolet Irradiation

Ozonation of several low molecular weight organic compounds under ultraviolet irradiation was studied. Nine compounds were identified as reaction products of the ozonation of phenol which was promoted by the simultaneous use of ozone and ultraviolet irradiation. In the case of several organic compounds having carbon numbers from one to six, the removal of total organic carbon (TOC) by this simultaneous use was higher than by either the ozone oxidation method or the ultraviolet irradiation method for all the compounds.     

pH Effect on Ozonation of Ampicillin: Kinetic Study and Toxicity Assessment

Ampicillin (AP) is a penicillin-type antibiotic and one of the most widely used bacteriostatic antibiotics in human and veterinary medicine. A kinetic study was performed under different pH conditions (5, 7.2, and 9) to determine the degradation efficiency of AP by ozonation. The second-order rate constants for the direct reaction of AP with ozone were measured to be 2.2 ?5.4×10⁵ M^?1s^?1 under the pH conditions tested. The rate constants were greater at higher pH. The potential toxicity of the AP intermediates formed after ozonation under the various pH conditions were examined using a bioluminescence assay on Vibrio fischeri species. The biodegradability of the AP degraded products was also determined by measuring the BOD₅/COD of the ozonated samples under the different pH conditions. A lower biodegradability and acute toxicity was observed at the lowest pH (pH 5). These results suggest that higher pH conditions are needed for the removal of AP by ozonation in order to mitigate the residual toxicity that can remain even after complete removal of the parent compound by ozonation.     

Ozonation and Precipitation for Treatment of Bleachery Effluents from Pulp Mills

Results from precipitation of an oxygen/peroxide-bleachery effluent from pulp mills with and without preozonation are presented. Reductions in DOC levels by about 60% were achieved at the pH optimum of 5.5 at an AI/D0C ratio of 0.25 g/g. Increasing alum dosages did not improve the elimination. Ozonation at pH 2 reduced COD, DOC, UV and color levels, while under alkaline conditions an increase of color could be obtained. This effect, based on a polymerization of organics, could be improved at low ozone dosages, by reducing the ozone dosage rate, elevating the pH up to 11 and diluting the wastewater. However, the shift towards high and low molecular weight fractions indicated competing degradation reactions, which counteract a suggested improvement of precipitation by preozonation.     

Ozonation Impact on Degradation and Toxicity of Non-Ionic Surfactants

Aqueous solutions of five selected non-ionic surfactants: Triton (i-octylphenolethoxylates), Tergitol (2,6,8-trimethyl-4-nonanoloxethylates), Symperonic (n-nonylphenol-oxethylates) and Brij (fatty alcohol ethoxylates) were investigated in this study. Using the bioluminescent bacteria Vibrio fischeri the toxicity of the surfactants solutions were determined. An attempt was made to relate rather low biodegradability of nonionic surfactant solutions measured by the BOD₅/COD ratio (ranging from 1 to 17%) to their toxicity. The ozonation process was carried out in a 1.5 dm³ stirred cell reactor equipped with two ozone detectors. The following parameters were analyzed: pH, COD, BOD₅, DOC, TOC, polarography as well as UV spectrum. The positive effect of ozonation, represented by decay of UV absorption, was visible in almost complete destruction of the surfactants, with exception of Triton X-705 (only 65% degradation after absorption of 2000 mgO₃/dm³). The most striking results were obtained in toxicity tests for ozonated solutions of the non-ionic surfactants – an increase of the bacterial growth inhibition (1.5 to 4 times increase in toxicity due to ozonation). The obtained results were discussed taking into account the literature and our own experimental data on mechanisms of ozonation and biodegradation of non-ionic surfactants of the Triton-type and similar chemical structures.     

Ozonation of NSAID: A Biodegradability and Toxicity Study

This work deals with the biodegradability and toxicity of three non-steroidal anti-inflammatory drugs (NSAID) (diclofenac, ibuprofen and naproxen) treated by ozonation. The results show that the total removal of 200 mg L^?1 of diclofenac and 100 mg L^?1 of naproxen is possible using an ozone dose of 0.20 and 0.04 g L^?1, respectively. For 200 mg L^?1 of ibuprofen, 90% removal is achieved using an ozone dose of 2.3 g L^?1. The BOD₅/COD ratio, the Zahn-Wallens test and EC₅₀ toxicity test (Microtox) are chosen as biological and toxicity indicators of NSAID intermediates. The evolution of BOD₅/COD ratio during 1 hour of treatment is evaluated and the results show that ozonation improves the biodegradability for the three NSAID treated solution. The Zahn-Wellens test for diclofenac and ibuprofen solutions shows that biological mineralization, after 28 days, is higher for diclofenac than for ibuprofen solution. According to the Microtox test, the treatment with ozone removes the toxicity of the naproxen solution. Taking into account the results obtained with the biocompatibility tests it could be assumed that ozonation is an adequate treatment for removal NSAID in aquatic medium, and the ozonated effluents could be post-treated in a biological wastewater facility.     

Effect of Ozonation on Activated Sludge Solubilization and Mineralization

New strategies for sludge stabilization and mineralization need to be developed since the use of sludge in agriculture is debatable and sludge incineration cannot be a systematic solution. Minimization of sludge production should be preferred. In this work, the effect of ozone on activated sludge solubilization and mineralization during batch experiments is assessed by establishing carbon and ozone mass balances. After extended ozonation of the sludge, more than 90% of the particulate carbon is modified. Depending on the experimental conditions, from 15 to 50% is found in a soluble form and from 35% to 95% was mineralized. The VSS/SS ratio decreases from 86% to less than 50% illustrating the sludge mineralization. The initial rate of ozone consumption by the sludge is very high (estimated value: 30 mgO₃/g VSS.min) and corresponds to high rates of carbon solubilization and mineralization. More than 50% of the carbon obtained after ozonation is found to be readily biodegradable using a short-term BOD procedure.     

Ozonation Dynamics and Its Implication for Off-Gas Ozone Control in Treating Pulp Mill Wastewaters

Ozonation of biologically pretreated pulp mill wastewaters was studied using both bench and pilot scale fine bubble contactors to determine the oxidation efficiencies, mass transfer coefficients (k_La) and enhancement factors (E) due to the occurrence of chemical reactions. A sensitivity analysis based on the measured process parameters was then used to reveal the interrelated effects of key factors on off-gas ozone concentrations. It was shown that the removal efficiencies of color and AOX were simply related to the amount of utilized ozone, regardless of variation of other operating conditions. Furthermore, the rate of absorption fell within the fast or instantaneous kinetics regimes due to the occurrence of rapid chemical reactions. The Ek_La values were found to vary substantially during the course of ozonation, indicating that the enhancement factors were not only affected not only by operating conditions but also by wastewater characteristics. To effectively control the off-gas ozone emission, measures should be taken to minimize the backmixing, use a counter-current flow arrangement and provide adequate contact time.     

苯酚、邻甲酚、2，6─—二甲酚三元体系的分离研究之一（间歇精馏）

通过间歇精馏分离苯酚、邻甲酚、２，６─—二甲酚三元体系。精馏塔采用高效不锈钢三角形填料，填料装填高度１２００ｍｍ，塔板约５５块，回流比１０，真空度约２．６７ｋｐａ，苯酚采出率为８７％（含量≥９８％），邻甲酚采出率为８１．４％（含量＞９９％）。     

Degradation of Aqueous Phenol and Chlorinated Phenols by Ozone

The degradation of phenol and its chlorinated derivatives with ozone is studied. The studied compounds are phenol (Ph), 4-chlorophenol (4-CPh) and 2,4-dichlorophenol (2,4-DCPh). The kinetic performances of each phenolic compound and their model mixture are examined. The pH influence on the decomposition dynamics for different phenolic compounds in the range 2–12 is investigated. The increase of the decomposition rate under increasing pH was observed. In the pH range studied, phenol and chlorophenols ozonation proceeds rapidly. The UV absorbency is used for the preliminary control of the degree of decomposition. The HPLC analysis is used to identify intermediates and final products formed during ozonation. It is shown that the basic intermediates are muconic and fumaric acids, malonic and maleic acids, catechol and hydroquinone. The final products are oxalic acid and formic acid. In the case of alkaline media, the principal final product is oxalic acid. Furthermore, intermediates and final decomposition products obtained at different pH are compared. According to the results obtained, the possible mechanism of ozonation by the reaction of hydroxylation and dechloration in the early stage is proposed. The BOD₅/COD ratio is used as a biodegradability measure for the comparison of biodegradability of initial compounds and final products composition.     

The Preozonation of Phenolic Aqueous Solution and Its Effect on the Improvement of Coagulation Treatment

Phenolic solutions are difficult to treat with coagulation processes because phenol is well soluble in water. However, with suitable preozonation, the ozonized organic components can be removed more effectively by coagulation processes. In order to avoid excessive preozonation, a good control on the degree of preozonation is crucial for practical applications. The degree of preozonation of phenolic solution was evaluated by measuring the phenol decomposition rate, ADMI value and ozone outlet concentration during the ozonation. Three characteristic times were observed, namely (1) ADMI value reaches the peak value during preozonation, (2) the ozone outlet concentration starts increasing, and (3) the ADMI value reaches the discharge standard (500 value, EPA Taiwan). These characteristic times provide the useful means as real-time control parameters on the extent of preozonation. The results of HPLC and GPC show that phenol is almost completely decomposed after 43?min of preozonation. The major components after preozonation are oxalic acid and coupling compounds. The preozonized solution, containing phenol decomposition products, was then subjected to coagulation treatments. The coagulation behavior of preozonized solution is dependent on the extent of preozonation. Three types of coagulant were investigated, namely alum, ferric chloride (FeCl₃) and poly aluminum chloride (PAC). Both PAC and FeCl₃ are effective coagulants for COD removal. As an example, phenol solution (initial phenol concentration=300?mg/L, C _{O 3},i=20?mg/L) was preozonized for 50 minutes, followed by FeCl₃ coagulation treatment. After preozonation and coagulation processes, the total COD and ADMI removal rates are as high as 70% and 80%, respectively. Most of the coupling compounds and oxalic acid are removed by the coagulant.     

Catalytic Ozonation of Citric Acid by Metallic Ions in Aqueous Solution

Ozonation of citric acid in water catalyzed by different ions from the first row of transition metals (Mn²⁺, Co²⁺, Ti⁴⁺, Fe²⁺, Cu²⁺, Ni²⁺ and Zn²⁺) was investigated at room temperature. The results showed that at pH=2, where the decomposition of citric acid is negligible by only ozone, the following order of efficiency of metallic ions for the decomposition of citric acid by ozone, and also for the TOC removal, was obtained: Mn²⁺ > Co²⁺ > Ti⁴⁺ > Fe²⁺. Cu²⁺, Ni²⁺ and Zn²⁺ showed negligible efficiency under the same experimental conditions. At pH=5.5, Mn²⁺ and Co²⁺ showed slightly higher efficiency than at pH=2 while Ti⁴⁺ and Fe²⁺ showed insignificant effect at this pH value. On the other hand, at pH=7 the investigated catalysts showed no obvious catalytic efficiency for the decomposition of citric acid by ozone.     

Comparison between Ozonation and Photo-Fenton Processes for Pesticide Methomyl Removal in Advanced Greenhouses

So-called “Advanced Greenhouses” are a new approach to the concept of protected agriculture. Among other technological and structural improvements, these facilities give the possibility of recycling the irrigation surplus water, rich in lixiviates, salts, pesticides and its metabolites. After many cycles, the current is so concentrated on those substances that it becomes necessary for the presence of a membrane separation stage which brine, highly concentrated on those named pollutants, has to be treated before being sent to the public sewage system. Advanced Oxidation Processes, among other chemical treatments, can be considered an alternative to process this current effluent. In this work, concentrated aqueous solutions of methomyl as model pesticide (200 mg·L^?1) have been subjected to two of those processes: ozonation and photo-Fenton reaction. Analysis of the elimination of the pesticide itself and the grade of mineralization achieved have shown how, while the ozonation is the most effective process decomposing the pesticide (eliminating the total concentration in 60 minutes), the photo-Fenton reaction mineralizes successfully the 40% of the total organic load (the ozonation only can cope with 20%) but only decompose a 40% of the pesticide. Evolution of biodegradability and toxicity of the effluent along both processes was also analyzed. Intermediates generated both by ozonation and photo-Fenton did not increase the biodegradability of the treated effluents. Nevertheless, while acute toxicity just after 15 minutes of treatment with ozone is notably higher than for raw solution, and it is maintained till the end of the experiment (120 min), though, toxicity along photo-Fenton reaction has two growing and decreasing regions, always shows lower values than the provoked during ozonation. None of the two assayed processes has been proved to increase biocompatibility of highly concentrated methomyl solutions.     

Sequential Ozonation and Biological Oxidation of Wastewaters: A Model Including Biomass Inhibition by Residual Oxidant

We modeled the potential impact of a residual oxidant (ozone in the present case, known to be a strong bactericide) on the performance of a combined chemical and biological water treatment. This model is fashioned by adapting a recent model for the kinetics of ozone disinfection to an activated sludge system performing in the presence of ozone residuals. Our new model allows prediction of the bioreactor performance under different substrate loadings and residual oxidant concentrations, helping to identify regimes where air stripping would be necessary before the second step.     

A Kinetic Investigation on the Ozonation of Glycerol and its Oxygenated Derivatives

The ozonation of glycerol and its main oxygenated derivatives is studied aiming at evaluating the possibility to convert them into valuable products. The direct ozonation of glycerol results into a mixture of its oxygenated derivatives. In some cases the use of ozone to convert them into valuable products proceeds with good selectivity. A kinetic study to estimate the kinetic constants of ozone attack to the main glycerol oxygenated intermediates is carried out. The data found are in keeping with the few values found in the literature for alcoholic groups by ozone.     

Comparison of Ozone-based and other (VUV and TiO2/UV) Radical Generation Methods in Phenol Decomposition

The degradation reaction kinetics and chemical mechanism of phenol decomposition by ozonation, TiO₂-photocatalysis and vacuum ultraviolet (VUV) photolysis were investigated. The concentration dependences of the aromatic and aliphatic intermediates and the TOC content were compared as a function of the phenol conversion. The concentration profiles and the TOC curves obtained with each method were very similar. The results suggest a similar chemical mechanism for the transformation of phenol irrespective of the starting active component (a positive hole on the surface of the catalysts, a VUV photon, ozone or the hydroxyl radical).