The removal of estrogenic activity and control of brominated by-products during ozonation of secondary effluents

The purposes of this study were to investigate the behavior of brominated by-products, such as bromate ion and total organic bromide, formed during ozonation for the removal of estrogenic activity in sewage effluents and to propose operation parameters for the ozonation process. It is necessary to reduce the E(2) equivalent concentration of estrogenic activity in secondary effluent treated by 90% of the initial one. To do so, ozonation until dissolved ozone concentration increased to 0.1mg/L (which corresponds to approximately 1mg O(3)/mg DOC(0) [consumed ozone per initial DOC] of consumed ozone for the effluent in this study) is proposed as an operation parameter for ozonation without the formation of brominated by-products.     

Study of catalyzed ozonation for advanced treatment of pulp and paper mill effluents

Ozonation and catalytic ozonation (TOCCATA process) were used as tertiary treatments of wastewaters from three different pulp and paper mills. Laboratory batch experiments were conducted to assess the efficiency of each oxidation system for removal of organic matter. The investigations measured ozone consumption rate, variations in chemical oxygen demand (COD), total organic carbon (TOC), suspended solids (SS) and molecular weight distribution with contact time. For conventional ozonation, ozone consumption rate was dependent on the nature of the effluent. Organic matter elimination occurred both by oxidation and precipitation. Precipitation played a major role on TOC removal varying with the effluent, and was responsible for production of high final SS concentrations. However, the effluent type did not affect the ozone consumption rate for TOCCATA-catalyzed reactions. Using TOCCATA, it was shown that organic matter was removed through steady conversion of organic carbon to carbon dioxide. Finally the two oxidation systems were compared with respect to their impact on molecular weight distribution. A total removal of the two initial fractions of compounds (high and low molecular weights) was observed with two effluents. With the third effluent, only the initial fraction of low molecular weight compounds was removed by the two oxidizing systems. The results showed that ozonation and TOCCATA-catalyzed ozonation could achieve removals of COD of 36-76%. Depending on the effluent type, the amount of ozone consumed per gram of COD removed was lower for conventional or for catalytic ozonation.     

利用同步臭氧氧化实现SBR污泥减量的研究

将臭氧通入SBR反应器中进行同步臭氧氧化,考察了污泥的减量效果以及对出水水质的影响.结果表明:污泥产率随着臭氧投量的增加而减小,当臭氧投加量从零增加到O.04gO3/gSS时污泥产率从0.45 gSS/gSCOD减少到-0.04 gSS/gSCOD;同步臭氧氧化对SBR系统的出水水质没有显著影响,当臭氧投加量为0.03 gO3/gSS时系统对COD、NH4 -N、TP的去除率分别为92.5%、91.1%、80.5%.可见,同步臭氧氧化是实现污泥减量的有效方法.     

DOC removal by multi-stage ozonation-biological treatment

Multi-stage ozonation-biological treatment process for dissolved organic carbon (DOC) removal was evaluated to apply for drinking water treatment. Waters with different types of DOC were used, i.e. a reservoir water for drinking water supply, a secondary effluent from a municipal wastewater treatment plant and a solution of humic substances extracted from leaf mold. The multi-stage ozonation-biological treatment process was compared with conventional single-stage ozonation-biological treatment process. Amount of DOC removed in biological treatment was defined as amount of biodegradable dissolved organic carbon (BDOC) in influent of biological treatment. DOC removal in the multi-stage ozonation-biological treatment was higher than that in the conventional single-stage ozonation-biological treatment with the same total ozonation time for the reservoir water and humic substances solution. Moreover, three- or four-stage ozonation for 5 min followed by biological treatment (total ozonation time 15 or 20 min) showed higher removal of DOC than the single-stage ozonation (60 min) and biological treatment. The higher DOC removal in the multi-stage treatment was due to the production of BDOC by ozonation. The long-term ozonation was not effective to produce BDOC because most of ozone was utilized to oxidize BDOC produced in the early stage of ozonation. In the multi-stage treatment, ozonation was effective to decompose refractory DOC and to produce BDOC because BDOC was removed by biological treatment. However, multi-stage ozonation-biological treatment was not effective for the secondary effluent. The reason seems to be high concentration of ozone scavengers in that water and low reactivity of DOC for ozone.     

Removal of pharmaceuticals and kinetics of mineralization by O(3)/H(2)O(2) in a biotreated municipal wastewater

The ozonation of an effluent from the secondary clarifier of two Municipal Wastewater Treatment Plants was performed by using alkaline ozone and a combination of ozone and hydrogen peroxide. Alkaline ozonation achieved only a moderate degree of mineralization, essentially concentrated during the first few minutes; but the addition of hydrogen peroxide eventually led to a complete mineralization. The evolution of total organic carbon (TOC) as a measure of the extent of mineralization and the concentration of dissolved ozone were analyzed and linked in a kinetic model whose parameter represented the product of the exposure to hydroxyl radicals and the kinetic constant of indirect ozonation. This rate parameter yielded the highest values during the first part of O(3)/H(2)O(2) runs. The kinetic constant for the decomposition of ozone at the end of the run was also measured and computed for the non-oxidizable water matrix and yielded essentially the same values regardless of whether or not hydrogen peroxide was used. A group of 33 organic compounds, mainly pharmaceuticals and some relevant metabolites present in the wastewater effluents, were evaluated before and after the ozonation process using a liquid chromatography-hybrid triple-quadrupole linear ion trap system (LC-QqLIT-MS). The results demonstrate that the ozonation degrades these compounds with efficiencies of over 99% in most cases, even under low mineralization conditions in alkaline ozonation.     

蜂窝陶瓷催化臭氧氧化处理饮用水中试

在北京市某净水厂进行了臭氧催化氧化处理滤后水的中试，对各种操作条件下蜂窝陶瓷催化臭氧氧化／颗粒活性炭过滤工艺的净水效果进行了考察。结果表明，与臭氧单独氧化相比，臭氧催化氧化反应器中有较高的溶解性臭氧浓度，对天然有机物（NOM）及总有机物（TOC）的去除效果较好，三氯甲烷生成潜能（CHCl3FP）较低。臭氧催化氧化的后续活性炭滤柱上的生物量较多，出水TOC、UV254及CHCl3FP值也均低于臭氧单独氧化的后续活性炭滤柱出水。     

Influence of ozonation on the in vitro mutagenic and toxic potential of secondary effluents

Reclamation of municipal effluents by advanced treatment processes is an attractive perspective for facing certain water shortage problems. However, the application of tertiary techniques should be thoroughly examined for their potential hazardous effects. Ozonation is an efficient chemical oxidation method, often used in wastewater reclamation, which may result in by-products that may alter the toxic and mutagenic properties of effluents. In this study, Ames test and Microtox test were used for the evaluation of ozonation efficiency to upgrade secondary effluents quality. In general, the toxic response and mutagenic effect without metabolic activation of test species were influenced mainly by the ozone dose and ozonation duration, whereas the mutagenic effect with metabolic activation was influenced mainly by ozone dose, indicating that ozone conditions strongly affect the formation of by-products. In most cases, the toxicity was increased and reached up to 100% (in relation to that of secondary effluent) after ozonation with 8.0 mg O₃/L for 5 min. On the contrary, in most cases the mutagenic activity towards strain TA98 without metabolic activation was reduced, when ozone dose and contact time increased. However, the mutagenicity was also increased after ozonation at low ozone doses and for contact times less than 5 min. The mutagenic activity of treated effluents towards strain TA98 with metabolic activation remained about the same or was reduced, compared to that of secondary effluent, and was even eliminated after ozonation with 8.0 mg O₃/L for contact times higher than 5 min.     

Combined biological and ozone treatment of log yard run-off

Batch biological treatment of log yard run-off reduced biochemical oxygen demand (BOD), chemical oxygen demand (COD) and tannin and lignin (TL) concentration by 99%, 80%, and 90%, respectively. Acute (Microtox) toxicity was decreased over treatment, from an initial EC50 of 1.83% to a value of 50.4% after 48 h of treatment. Kinetics of biodegradation were determined using respirometry and fitted using the Monod and Tessier model. For the Monod model the maximum substrate uptake rate, and Ks values determined were 0.0038 mg BOD/mgVSS min, and 1.4 mg/L, respectively. The efficacy of ozone as a pre- and post- biological treatment stage was also assessed. During ozone pretreatment, TL concentration and acute toxicity were rapidly reduced by 70% and 71%, respectively. Pre-ozonation reduced BOD and COD concentration by < 10%, however a larger fraction of residual COD was non biodegradable after ozonation. Biologically treated effluent was subjected to ozonation to determine whether further improvements in effluent quality could be achieved. A reduction in COD and TL concentration was observed during ozonation, however no further improvement in toxicity was observed. Ozonation increased BOD by 38%, due to conversion of COD to BOD.     

Wastewater disinfection by ozone: main parameters for process design

Wastewater disinfection by ozone was investigated at pilot scale on different wastewater effluents. Variations in operating conditions showed that a very low hydraulic retention time (2 min) was sufficient for efficient fecal coliform inactivation, provided a sufficient ozone dose was transferred to the effluent. Therefore, the transferred ozone dose appeared to be the critical parameter for the design of wastewater disinfection. As a consequence, the "Ct" approach commonly applied in drinking water treatment should not be used for wastewater ozonation. Design parameters of ozonation were proposed for two types of regulations, and for effluents of different qualities. It was demonstrated that only with an efficient filtration step one can meet stringent standards such as the California Title 22 criteria. In all cases, viruses were totally inactivated; consequently, viruses do not constitute a limiting factor in wastewater disinfection by ozone. The standard drinking water model failed to match the experimental data obtained on real wastewater effluents. A modified approach was successfully developed, based on the simultaneous consumption of ozone by the microorganisms and the organic matrix.     

Dynamic behavior of ozonation with pollutant in a countercurrent bubble column with oxygen mass transfer

The dynamic behavior of ozonation with pollutants in a countercurrent bubble column is studied for the model establishment. Bubble columns have been widely used for an ozonation system in the plants and laboratories. In addition, a countercurrent bubble column has been commonly recommended than a cocurrent one because it has a higher ozone transfer efficiency. Therefore, the investigation of this paper focuses on the countercurrent bubble column. As an ozonation process starts, the gas mixture of ozone and oxygen is introduced into the bottom of a column, and then transferred into the liquid. The pollutants in the wastewater are eliminated subsequently via oxidation by the dissolved ozone. There certainly exists a temporary and unsteady period before the ozonation system reaches steady state. However, available ozonation models employed to describe ozone and pollutant profiles have commonly been developed for steady state. The treating qualities of wastewater in the early stage of ozonation are usually not predicted, and the time required for the steady-state establishment remains to be determined. Moreover, oxygen mass transfer is usually neglected in previous ozonation models so that the increase of dissolved oxygen is uncertain. These information is desirable for the proper design and operation of ozonation system in a bubble column. Thus, the aim of this study is to model and investigate the dynamic processes of ozonation with pollutants including oxygen mass transfer. The dynamic axial dispersion model proposed is employed to predict the variation of the ozone, pollutant, and oxygen concentrations profiles. The validity of the model was demonstrated by comparing the predicted results with the experimental data. The o-cresol was chosen as the model pollutant. The temporal concentration variations of the residual o-cresol and dissolved oxygen in the effluent liquid, and the off-gas ozone in the free volume were measured accordingly. Furthermore, the variation of the enhancement factor of ozone and the amount of off-gas were predicted. Note that it usually needs 2-5 hydraulic retention times to approach steady state under the conditions of this study. Further, the effects of dimensionless system parameters on the performance of the ozonation processes are examined. As a result, the proposed dynamic model of ozonation with pollutants is useful for proper prediction of the variables of an ozonation system in a countercurrent bubble column.     

Stabilized leachates: ozone-activated carbon treatment and kinetics

Ozone has been used as a pre-oxidation step for the treatment of stabilized leachates. Given the refractory nature of this type of effluents, the conversion of some wastewater quality parameters has been moderate after 1 h of ozonation (i.e. 30% chemical oxygen demand (COD) depletion). Ozone uptake was calculated in the interval 1.3–1.5 g of ozone per gram of COD degraded. An optimum dose of ozone has been experienced in terms of biodegradability of the processed effluent (60 min of treatment, 1×10⁻³ molL⁻¹ ozone inlet feeding concentration and 50 Lh⁻¹ gas flow-rate). pH and other typical hydroxyl radical generator systems exerted no influence on the efficiency of the process, suggesting the negligible role played by the indirect route of oxidation (generation of hydroxyl radicals). The ozonated effluent was thereafter treated in a second adsorption stage by using a commercial activated carbon. Removal levels up to 90% of COD in approximately 120 h were experienced for adsorbent dosages of 30 gL⁻¹. Both steps, the single ozonation and the adsorption stage have been modelled by using different pseudoempirical models.     

Ozonation des amines dans l'eau ozonation of amines in aqueous solutions

Amines are nitrogenated compounds which may be found in water and in the atmosphere. The use of ozone for micropollution removal is growing; the aim of our study is to specify the behaviour of these compounds during ozonation.The studied amines are: methylamine. ethylamine, propylamine, cyclohexylamine, dimethylamine. N-methyl-butylamine and trimethylamine; the tests are classified in two groups.The first group of tests is carried out with concentrated aqueous solutions (7% in weight) to find the ozonation products. the identifications are carried out by the coupling gas chromatography with mass spectroscopy. The second group of tests is carried out with diluted aqueous solutions concentrations (10 ppm) are of which nearer to the usual effluent concentrations than the concentrated solutions ones.1. The identifed compounds in concentrated solution (Table 1) lead us to propose a reaction diagram (Fig. 3) for the ozonation of primary, secondary, tertiary amines. In any case, we notice an electrophilic attack of ozone on nitrogen lone pair of electrons, with: oxidation products of nitrogen (hydroxylamines, oximes and nitrogen oxides) and of carbon in α position (amides): breakdown products from initial molecules (aldehydes, ketones and acids) associated with the formation of mineral nitrogen (NO₂^-. NO₃^-) condensing products as polyamide types. Figure 5 shows the evolution of the different products of ozonation in terms of the ozone consumption for the cyclohexylamine instance.2. In diluted solutions, the oxidation rate of the various amines is linked to the available quantity of ozone (Figs 1 and 2): we find aldehydes, carboxylic acids and nitrates as ozonation products. According to these results, ozone is the choice oxidant for the treatment of industrial sewages and malodorous gas containing amines. The ozone used for the production of drinking water contributes to the removal of this kind of pollution.     

Elimination of resin acids by advanced oxidation processes and their impact on subsequent biodegradation

Wood pulping and paper production generate a considerable amount of wastewater, containing many pollutants among them resin and fatty acids. Resin acids contribute substantially to effluent toxicity and were identified to be detrimental to microorganisms of activated sludge and in particular to bacteria in anaerobic wastewater treatment system and other forms of aquatic life. The objective of the present study was to check the applicability of the ozone and advanced oxidation processes (AOPs) to eliminate resin acids from aqueous solutions and to determine the ozone dose required. Furthermore, an investigation of the influence of the oxidation methods on subsequent biological destruction of the byproducts was performed. Aqueous solution of the resin acids: abietic, dehydroabietic and isopimaric acids with different initial composition were subjected to ozonation or AOP processes at different ozone doses. After ozonation or advanced oxidation pretreatment the model solutions were biodegraded in aerated vessels containing activated sludge. During ozonation of the resin acids aqueous solutions the resin acids were almost eliminated, however the reduction of chemical oxygen demand (COD) was rather low. The ozone dose required to obtain reduction of resin acids >90% was in the range of 0.1-0.7mgO(3)/mgCOD, depending on the composition and concentration of model solutions. The toxicity of ozonated resin acids solutions decreased with increasing applied ozone dose up to about 0.3-0.5mgO(3)/mgCOD, thereafter increased. Ozonation and other AOP processes did not increase the rate of biodegradation of resin acids model solutions in aerated activated sludge systems compared to not pretreated solutions.     

Mineralisation of coloured aqueous solutions by ozonation in the presence of activated carbon

The degradation of organic matter in coloured solutions of different classes of dyes by ozonation in the presence of activated carbon is investigated. The kinetics of the decolourisation and mineralisation of three different dyes solutions (CI Acid Blue 113, CI Reactive Red 241 and CI Basic Red 14) were studied in a laboratory scale reactor by three different processes: adsorption on activated carbon, oxidation with ozone and ozonation in the presence of activated carbon. The mineralisation of the solutions was followed by measuring the total organic carbon (TOC). Under the experimental conditions used in this work, activated carbon was not capable of completely removing the colour of the solutions in reasonable time. On the other hand, ozonation quickly decolourised all the solutions, but satisfactory removal of TOC was never achieved by this process. The combination of activated carbon with ozone enhanced the decolourisation of the solutions and especially the mineralisation of the organic matter. Activated carbon acts both as an adsorbent and as a catalyst in the reaction of ozonation. The surface chemistry of the activated carbon is an important parameter; it was observed that basic samples improve TOC removal. The main conclusions of this work were validated by treating a real textile effluent collected after the conventional biological treatment.     

Physicochemical aspects of disinfection of water by means of ultrasound and ozone

20 kHz-ultrasonic waves intensify the ozonation process in regard to disinfection of microorganisms, as well as to oxidation of organics. Ultrasonic treatment of effluent from biological sewage plant, reduced the sterilization dose of ozone with 50%, and increased the half order rate constant of decoloration of Rhodamine B with 55%.The phenomena is attributed to the action of two physicochemical mechanisms. (1) Ultrasound decomposes ozone causing augmentation of the activity of free radicals. (2) Simultaneous ultrasonic treatment enhances the aeration constant, (K_Lα-value). Both mechanisms increase the gas liquid ozone transfer and the utilization of the applicated ozonated gas.It is verified that free radicals are the proper disinfective and oxidative agents in ozonation and sonozonation. Ozone molecules act as precursors and may in themselves be relatively nontoxic.     

Integrated ozone and biotreatment of pulp mill effluent and changes in biodegradability and molecular weight distribution of organic compounds

The overall effectiveness of integrating ozonation with biological treatment on the biodegradability enhancement and recalcitrant organic matter (ROM) removal from pulp mill alkaline bleach plant effluent was investigated. Ozonation was performed in a semi-batch bubble column reactor at pH of 11 and 4.5. Batch biological treatment was conducted in shake flasks. Samples obtained during the treatments were monitored for BOD₅, COD, TOC, and molecular weight distribution. At an ozone dosage of 0.7-0.8 mg O₃/mL wastewater, integrated treatment showed about 30% higher TOC mineralization compared to individual ozonation or biotreatment. Ozone treatment enhanced the biodegradability of the effluent (monitored as 21% COD reduction and 13% BOD₅ enhancement), allowing for a higher removal of pollutants. The conversion of high molecular weight (HMW) to low molecular weight (LMW) compounds was an important factor in the overall biodegradability enhancement of the alkaline effluent. The overall biodegradability of the LMW compounds did not change over the course of ozonation, but it increased from 5% to 50% (measured as COD removal) for the HMW portion. Ozonation at pH of 11 was more effective than that at pH of 4.5 in terms of generating more biodegradable compounds.     

Effects of ozone pre-treatment on diclofenac: Intermediates, biodegradability and toxicity assessment

Diclofenac (DCF), a common analgesic, anti-arthritic and anti-rheumatic drug, is one of the most frequently detected compounds in water. This study deals with the degradation of diclofenac in aqueous solution by ozonation. Biodegradability (BOD₅/COD ratio and Zahn-Wellens test), acute ecotoxicity and inhibition of activated sludge activity were determined in ozonated and non-ozonated samples. Liquid chromatography coupled with time-of-flight mass spectrometry (LC/TOF-MS) was used to identify the intermediates formed in 1 h of ozonation. Eighteen intermediates were identified by these techniques and a tentative degradation pathway for DCF ozonation is proposed.Experimental results show that ozone is efficient at removing DCF: > 99% removal (starting from an initial concentration of 0.68 mmol L^− 1) was achieved after 30 min of ozonation (corresponding to an absorbed ozone dose of 0.22 g L^− 1, which is 4.58 mmol L^− 1). However, only 24% of the substrate was mineralized after 1 h of ozonation. The biodegradability, respiration inhibition in activated sludge and acute toxicity tests demonstrate that ozonation promotes a more biocompatible effluent of waters containing DCF.     

Inactivation of Escherichia coli by ozone under bench-scale plug flow and full-scale hydraulic conditions

To determine the disinfection efficacy of ozonation, water companies can apply several disinfection calculation methods. The goal of this study was to evaluate the use of the T10 and continuous stirred tank reactor (CSTR) method to extrapolate inactivation rates of ozone sensitive microorganisms observed in laboratory tests to full-scale ozonation in drinking water treatment. The inactivation efficacy of the ozonation at the Amsterdam water treatment works was assessed by determining Escherichia coli concentrations in large volume samples before and after ozonation over a period of 1 year. The inactivation of dosed E. coli WR1 was tested in a bench-scale dissolved ozone plug flow reactor (DOPFR) on the same feed water as the full-scale ozonation in which a concentrated ozone solution in Milli-Q water was dosed. Applying the T10 method on the inactivation rates observed in the DOPFR strongly overestimated the inactivation capacity of the full-scale ozonation. The expected inactivation based on the CSTR method (LT2ESWTR) approached the observed inactivation at full-scale. Therefore, the CSTR method should be preferred to calculate inactivation of ozone sensitive organisms such as E. coli, viruses, Giardia and Campylobacter by full-scale ozonation.     

Oxidation of metal-diethylenetriaminepentaacetate (DTPA)--complexes during drinking water ozonation

This study investigates the oxidative transformation of diethylenetriaminepentaacetate (DTPA), a synthetic ligand, during drinking water ozonation. The rate coefficients for the reactions of CaDTPA3- and ZnDTPA3- with ozone were determined to be 6200 and 3500 +/- 150 M-1 s-1, respectively. The reactivity of Fe(III)DTPA2- towards ozone was found to be much lower (< 10 M-1 s-1), but near neutral pH the reactivity of the Fe(III)-complexes is dominated by [Fe(III)(OH)]DTPA3-. For the reaction of Fe[(III)(OH)]DTPA3- with ozone a rate coefficient of 2.4 +/- 0.2 x 10(5) M-1 s-1 was measured. The rate coefficients of the reactions of the ZnDTPA- and Fe(III)DTPA with OH radicals have been determined by a competitive method as 2.4 +/- 0.4 x 10(9) and 1.5 +/- 0.1 x 10(9) M-1 s-1, respectively at pH = 7. The degradation of low concentrations of DTPA complexes during ozonation was investigated in natural waters under drinking water relevant conditions. Based on our findings CaDTPA3- and ZnDTPA3- are judged as easily degradable. Fe(III)DTPA complexes showed a somewhat lower reactivity, but were still typically degraded by one order of magnitude at ozone dosages of approximately 20 microM (1 mg L-1) in the three natural waters tested. Molecular ozone was found to be the major oxidant for the metal-DTPA complexes during ozonation.     

Spectroscopic study of degradation products of ciprofloxacin, norfloxacin and lomefloxacin formed in ozonated wastewater

This study addressed the formation and properties of degradation products of ciprofloxacin, norfloxacin and lomefloxacin formed during ozonation of secondary wastewater effluent containing these fluoroquinolone antibiotics. The generation of the degradation products was interpreted in the context of transformations of effluent organic matter (EfOM) tracked via absorbance measurements. The structures of 20 degradation products were elucidated for ciprofloxacin and norfloxacin, respectively. 27 degradation products were identified for lomefloxacin. The prevalent oxidation pathways were suggested based on the structures of the identified products formed in the absence and presence of the hydroxyl radical scavenger t-butanol. These pathways were largely similar for all studied fluoroquinolones and involved attacks on the piperazine ring and the quinolone structure. The quinolone ring remained intact in the presence of t-butanol thus indicating that this functional group could only be oxidized by OH radicals while the piperazine ring was readily oxidized by molecular ozone. The cleavage of the quinolone moiety that resulted in several identified degradation products occurred via the attack by hydroxyl radicals on the carbon-carbon double bond adjacent to the carboxylic acid group. Lomefloxacin had more diverse oxidation products due to the presence of a methyl group on its piperazinyl ring. The concentrations of the identified degradation products behaved non-monotonically as a function of ozone dose or treatment time, yet exhibited interpretable correlations versus changes of EfOM absorbance. Examination of these correlations allowed developing a novel approach for elucidating the transformations of fluoroquinolone antibiotics during ozonation.