Ozonation And AOP Treatment Of Phenanthrene In Aqueous Solutions

Phenanthrene is considered to be a hazardous pollutant and is listed as a priority pollutant by the U.S. EPA. This laboratory study was designed to investigate the degradation of phenanthrene in water solutions by ozone, by ozone in combination with hydrogen peroxide and UV-radiation and by UV-radiation only, to compare the efficiency of different oxidation processes at different values of pH = 3, 7 and 9. On the basis of kinetic curves of phenanthrene destruction, the chemical reaction rate constants were calculated. The results obtained confirmed that phenanthrene oxidation proceeds mostly with molecular ozone and the best method for reducing its concentrations is an ozonation in neutral medium. The rate of phenanthrene autoxidation is rather slow and does not depend on pH nor H₂O₂ addition. UV-radiation alone is also unable to reduce phenanthrene concentration significantly.     

The Disinfecting Action of Ozonated Water and of Hydrogen Peroxide/Silver Ions In Vitro

An in-vitro comparison was made between the disinfecting action of ozonated water and hydrogen peroxide/silver ion preparations using the “Quantitative suspension” test and Pseudomonas aemginosa. No microorganisms could be detected immediately after contact between ozonated water and the pseudomonadeae. In the case of the peroxide preparation, however, its action corresponded to that of aqua bidestillata (control experiment) and no disinfection had taken place. The use of hydrogen peroxide preparations in dental units for microbiological and toxicological reasons should therefore be reconsidered.     

Improvement in the Effectiveness of Ozonation of Drinking Water Through the Use of Hydrogen Peroxide

Addition of hydrogen peroxide to water during ozonation increases the rate of oxidation of organic compounds and ozone transfer. Coupling ozone with hydrogen peroxide can increase the efficiency of a drinking water treatment line, for example in removing THM precursors. To optimize this oxidation process, the quantity of hydrogen peroxide added and the point of injection must be carefully selected.     

Comparative Efficiency Of Three Systems (O3, O3/H2O2, and O3/TiO2) For The Oxidation Of Natural Organic Matter In Water

CATAZONE is a new process of heterogeneous catalytic ozonation in which water is ozonated in the presence of a solid catalyst composed of titanium dioxide. The efficiency of this O₃/TiO₂ system has been compared to the two well-known oxidant systems: ozone alone and ozone combined with hydrogen peroxide.

This comparison was undertaken on three models of natural organic compounds : an aquatic fulvic acid, a protein and a disaccharide. The first results showed the following order of relative efficiency: O₃/TiO₂ > O₃/H₂O₂ > O₃ as far as Total Organic Carbon (TOC) removal was concerned.     

Bactericidal Effectiveness of O3, O3/H2O2 and O3/TiO2 on Clostridium perfringens

The purpose of this research is to evaluate the bactericidal capacity of different Advanced Oxidation Treatments (AOTs) based on ozone: ozone, ozone/hydrogen peroxide and ozone/titanium dioxide on a wild strain of Clostridium perfringens, a fecal bacterial indicator in drinking water. The dose of ozone consumed ranges from 0.6 mg L^?1 min^?1 to 5.13 mg L^?1 min^?1 depending on the process and on the sample. In the treatments combined with O₃, H₂O₂ dose utilized is 0.04 mM and TiO₂ dose, 1 g L^?1. In order to evaluate the influence of natural organic matter and suspension solids over the disinfection rate, treatments are performed with two types of water – natural water from Ebro River (Zaragoza, Spain) and NaCl solution 0.9%. To achieve 4 log units of inactivation, 3.6 mg O₃ L^?1 is necessary in O₃ treatment, 4.25 mg O₃ L^?1 in O₃/TiO₂ system and 2.7 mg O₃ L^?1 in O₃/H₂O₂ after processing the natural water. In NaCl solution, to get the same inactivation, 0.42 mg O₃ L^?1 is necessary in O₃ treatment, 1.15 mg O₃ L^?1 in O₃/TiO₂ system and 0.06 mg O₃ L^?1 in O₃/H₂O₂ process. Even though the three treatments studied have a high bactericidal activity due to the number of surviving bacteria decreases to non-detectable levels, O₃/H₂O₂ is the most effective system for eliminating C. perfringens cells in a lower contact time, followed by O₃ and finally O₃/TiO₂ system.     

Kinetic Study and Optimum Control of the Ozone/UV Process Measuring Hydrogen Peroxide Formed In-situ

This study was conducted to develop a kinetic model of the ozone/UV process by monitoring the trend of in-situ hydrogen peroxide formation. A specifically devised setup, which could continuously measure the concentration of hydrogen peroxide as low as 10 μg/L, was used. The kinetic equations, comprised of several intrinsic constants with semi-empirical parameters (k_chain and k_R3) were developed to predict the time varied residual ozone and hydrogen peroxide formed in situ along with the hydroxyl radical concentration at steady state,[OH°]_ss, in the ozone/UV process. The optimum ozone dose was also investigated at a fixed UV dose using the removal rate of UV absorbance at 254 nm (A₂₅₄) in raw drinking water. The result showed that the continuous monitoring of hydrogen peroxide formed in situ in an ozone/UV process could be used as an important tool to optimize the operation of the process.     

Effects Of Ozone-Hydrogen Peroxide Combination On The Formation Of Biodegradable Dissolved Organic Carbon

The effects of ozone and ozone/hydrogen peroxide on BDOC formation were studied with the “Ozotest” method, a laboratory technique that permits the assessment of oxidation efficiency. Oxidation treatments were performed on river water and sand filter effluent samples. Ozone consumption, reduction of UV absorbance, and BDOC formation were monitored during the experiments. The ratio of 0.35-0.45 mg H₂O₂ per mg O₃ used to degrade pesticides also was optimal for the oxidation of organic matter. BDOC formation versus ozone dose curves with ozone alone or ozone/peroxide system were similar. BDOC formation was optimum at an applied ozone dose of 0.5-1 mg O₃/mg C (contact time = 10 min). The ozone/peroxide system yielded lower BDOC values than ozone alone, a phenomenon related to differences in byproducts generated by the two oxidative systems. Moreover, reduction of the concentration of DOC was higher with ozone/hydrogen peroxide than with ozone alone. For both oxidant systems, BDOC formation occurred during the first minute of treatment.     

Ozone Versus Ozone/Peroxide Induced Particle Destabilization And Aggregation: A Pilot Study

This research compares the role of ozone and the conjunctive use of ozone plus hydrogen peroxide in particle destabilization and particle aggregation, and improvement in filtered water quality. Particle destabilization was observed at all doses of ozone and ozone/peroxide studied, whereas aggregation was observed with ozone only at lower doses (> 2 mg/L) and in conjunction with ozone/peroxide (all doses studied). As compared to alum alone, the ozone-plus-alum and ozone/peroxide-plus-alum treatments provided improved flocculation and better filtered water quality. In addition, each of these preoxidations significantly reduced alum requirements. Overall, in terms of particle destabilization and aggregation; i.e., effectiveness as a coagulation aid, Ozone/peroxide performed better than ozone.     

The Combination of Ozone/Hydrogen Peroxide and Ozone/UV Radiation for Reduction of Trihalomethane Formation Potential in Surface Water

Applied ozone dosages of 20, 25, and 30 mg/L to lake water utilized by the city of Shreveport, LA produced no significant reductions in trihalomethane formation potentials (THMFP). However, the addition of 20 mg/L of hydrogen peroxide and/or 0.67 W/L of UV radiation (254 nm) in combination with ozone produced decreases in THMFP of over 60% in 60 minutes. Smaller THMFP decreases were seen with shorter contact times. The use of H₂O₂ and/or UV in combination with O₃ increased the percentage of applied ozone consumed by the lake water (i.e., enhanced the ozone mass transfer) five times over simple ozonation.     

Effects of Ozone and Ozone/Hydrogen Peroxide on the Degradation of Model and Real Oil-Sands-Process-Affected-Water Naphthenic Acids

Naphthenic acids (NAs) are persistent compounds that contribute to the toxicity of oil sands process-affected water (OSPW). In this study, the effects of ozone and ozone/hydrogen peroxide on the NAs degradation in buffered water and OSPW were examined. Cyclohexanoic acid (CHA) was used as a model NAs compound in buffered water experiments at two different pHs, using radical scavengers. At pH 9, the addition of carbonate did not have any effect on CHA degradation. Additions of tert-butyl alcohol and tetranitromethane decreased the CHA degradation levels. For the OSPW experiments, degradation of acid-extractable fraction (AEF) and NAs was examined. Approximately 90% of AEF was oxidized in a semi-batch system. In a batch system, 99% of OSPW NAs were degraded. This study demonstrated that ozone and ozone/hydrogen peroxide could be suitable treatment processes for OSPW remediation.     

Organic matter removal in boiler feed water treatment of a power plant with ozone

The purpose of this work was to test the effectiveness of ozone as a treatment to remove organic matter of the boiler feed water of a power plant. In the experiments carried out in the power plant Endesa in As Pontes (Spain), chlorine was substituted for ozone in the pre‐treatment stage. The use of ozone reduced the organic content of the boiler feed water by an average 20% compared with chlorination and by 50% when ozone was combined with hydrogen peroxide. The latter treatment achieved an organic content in the boiler feed water of less than 40 μg C/L. The ozone treatment also reduced the content of trihalomethanes in the drinking water, produced by the same plant, to values in the range of 10 μg/L and even to undetectable values when ozone was combined with hydrogen peroxide, in spite of the postchlorination applied to this stream to ensure a disinfectant capacity though the distribution system.     

O3/H2O2 Treatment of Methyl-terf-Butyl Ether in Contaminated Waters: Effect of Background COD on the O3-Dose

The destruction of methyl-tert-butyl ether (MTBE) in contaminated waters by O₃/H₂0₂ process was studied and the influence background COD, alkalinity, and hydrogen peroxide and MTBE concentrations on process treatment efficiency and ozone dosage was investigated. The treatment efficiency was evaluated by an Efficiency Index, which is based on electrical energy requirement for ozone production. It was found that the treatment efficiency decreases linearly with increasing concentrations of MTBE at constant background COD and with background COD at constant MTBE concentration. A simplified kinetic scheme was presented to account for these observations.     

Performance evaluation of ozonation and an ozone/hydrogen peroxide process toward development of a new sewage treatment process—Focusing on organic compounds and emerging contaminants

Performance of ozonation and an ozone/hydrogen peroxide process under a new concept centering on ozonation and/or ozone/hydrogen peroxide processes in sewage treatment processes comprising only physical and chemical processes are discussed, with focus on the removal of matrix organic compounds and emerging contaminants. Matrix organic compounds of filtrated primary sewage effluents were removed to as low as 3.2 mgC/L in the ozone/hydrogen peroxide process at an ozone consumption of around 400 mg/L. Linear relationships between ozone consumption and removal amounts of organic compounds were observed, in which the amounts of ozone required to remove 1 mg of organic carbon were 9.5 and 8.3 mg (2.4 and 2.1 mol-O₃/mol-C) in ozonation and the ozone/hydrogen peroxide process, respectively. Ratios of hydroxyl radical exposure to ozone exposure were in the order of 10^–9 to 10^–8 for ozonation and 10^–7 to 10^–6 for the ozone/hydrogen peroxide process. Experiments and a kinetic evaluation showed that ozonation and/or the ozone/hydrogen peroxide process have high elimination capability for emerging contaminants, even in primary sewage effluent with the thorough removal of matrix organic compounds. Newly found reaction phenomena, the temporal increase and decrease of dissolved ozone and accumulation of hydrogen peroxide in the early stage of oxidation with the continuous feeding of hydrogen peroxide, were presented. Possible reaction mechanisms are also discussed.     

The Advanced Oxidation Process of Phenol Solution by O3/H2O2 in a Rotating Packed Bed

This article presents experimental investigation on the oxidative treatment of phenol in water by O₃/H₂O₂ in a rotating packed bed (RPB). It was found that the phenol degradation ratio increased with increasing rotation speed, initial pH value of phenol solution, and temperature. The degradation ratio of phenol had a peak value with increasing H₂O₂ concentration. The optimum operating conditions in this study were determined as an H₂O₂ concentration of 6.5 mM and a rotation speed of 1200 rpm. Phenol degradation ratio reached 100% at an initial phenol concentration of 40 mg/L in the O₃/H₂O₂ process.     

Removal Characteristics of Organic Pollutants in Sewage Treatment by a Pre-Coagulation,Ozonation and Ozone/Hydrogen Peroxide Process

The applicability of a sequential process of ozonation and ozone/hydrogen peroxide process for the removal of soluble organic compounds from a pre-coagulated municipal sewage was examined. 6–25% of initial T-COD_Cr was removed at the early stage of ozonation before the ratio of consumed ozone to removed T-COD_Cr dramatically increased. Until dissolved ozone was detected, 0.3 mgO₃/mgTOC₀ (Initial TOC) of ozone was consumed. When an ozone/hydrogen peroxide process was applied, additional COD_Cr was removed. And we elucidated that two following findings are important for the better performance of ozone/hydrogen peroxide process; those are to remove readily reactive organic compounds with ozone before the application of ozone/hydrogen peroxide process and to avoid the excess addition of hydrogen peroxide. Based on these two findings, we proposed a sequential process of ozonation and multi-stage ozone/hydrogen peroxide process and the appropriate addition of hydrogen peroxide. T-COD_Cr, TOC and ATU-BOD₅ were reduced to less than 7 mg/L, 6 mgC/L and 5 mg/L, respectively after total treatment time of 79 min. Furthermore, we discussed the transformation of organic compounds and the removal of organic compounds. The removal amount of COD_Cr and UV₂₅₄ had good linear relationship until the removal amounts of COD_Cr and UV₂₅₄ were 30 mg/L and 0.11 cm^?1, respectively. Therefore UV₂₅₄ would be useful for an indicator for COD_Cr removal at the beginning of the treatment. The accumulation of carboxylic acids (formic acid, acetic acid and oxalic acid) was observed. The ratio of carbon concentration of carboxylic acids to TOC remaining was getting higher and reached around 0.5 finally. Removal of TOC was observed with the accumulation of carboxylic acids. When unknown organic compounds (organic compounds except for carboxylic acids) were oxidized, 70% was apparently removed as carbon dioxide and 30% was accumulated as carboxylic acids. A portion of biodegradable organic compounds to whole organic compounds was enhanced as shown by the increase ratio of BOD/COD_Cr.     

Degradation Of Selected Herbicides In A Lowland Surface Water By Ozone And Ozone-Hydrogen Peroxide

The efficiency of ozone, and ozone in combination with hydrogen peroxide, for the degradation of five herbicides: Atrazine, Benazolin, Bentazone, Imazapyr and Triclopyr, under controlled laboratory conditions was investigated. Experiments were conducted at pH 7.5 in a bubble contactor column with a raw lowland surface water spiked with initial active ingredient concentrations of 2 μg/L. Mean consumed ozone doses were approximately 1, 2 and 3 mg O₃/L. Hydrogen peroxide was added simultaneously to the application of ozone in a series of six mass ratios, between 0.0 and 1.0, with each of the consumed ozone doses. The results demonstrated a greater but varying removal of all herbicides achieved with increasing consumed ozone and applied hydrogen peroxide doses.     

The Influence of H2O2 in Ozonation Treatment: Experience of the Water Supply Service of Florence,Italy

This paper reports on the use of ozone in the Water Supply Service of Florence (Italy). The addition of hydrogen peroxide at the end of ozonation treatment has proved particularly efficient for controlling bromates and brominated organic byproducts. Significant differences regarding the formation of oxygenated organic compounds were not observed.     

Enhanced Bactericidal Effect of O3/H2O2 Followed by Cl2

With the appearance of chlorine resistant microorganisms such as Cryptosporidium parvum and Giardia lamblia in drinking water, significant attention has been drawn to the sequential application of multiple disinfectants including ozone, chlorine dioxide, and UV as a primary disinfectant. However, few studies have reported about the inactivation behavior of ozone-based AOP (advanced oxidation process) or its sequential application combined with other disinfectants. This is especially important since ozone itself experiences difficulty in the inactivation of these pathogens, especially at low temperatures: This study investigates the enhanced inactivation of Bacillus subtilis spores by the presence of an OH radical in the O₃/H₂O₂ system and the synergistically enhanced inactivation in the application of the O₃/H₂O₂ system followed by Cl₂. The results suggest that the O₃/H₂O₂ process can be considered as one of the viable alternatives when O₃ alone does not satisfy the disinfection requirement.     

The Impact of Traces of Hydrogen Peroxide and Phosphate on the Ozone Decomposition Rate in “Pure Water”

To obtain an idea of the magnitudes of the ozone loss rates r_O3 in practical applications of ozone, an overall determination of the ozone decay profiles and rate constants was carried out in four different systems. These systems resemble different conditions for industrial application of ozone and the peroxone process, such as in the field of micro electronics, drinking water purification, disinfection, etc. Therefore, the behavior of ozone was monitored in the pH range from 4.5 to 9.0, in pure water and phosphate buffered systems in absence and presence of small amounts of hydrogen peroxide (10^?7 M to 10^?5 M H₂O₂). First the reproducibility of the ozone decay profiles was checked and from the various kinetic formalism tests, the reaction order 1.5 for the ozone decay rate has been selected. As expected, hydrogen peroxide increases the decay rates. In pure systems, added concentrations of 10^?7M H₂O₂ already cause a remarkable acceleration of the ozone decay in the acidic and neutral pH range compared to the pure systems. However for alkaline pH conditions almost no effect of the low hydrogen peroxide concentrations was noticed. Contradictory to literature data, in the absence of hydrogen peroxide, ozone displays faster decays in the buffered systems of low ionic strength of 0.02 compared to pure water. This acceleration is more pronounced for acidic pH conditions. Low concentrations of phosphate may indeed accelerate the ozone decay in the presence of organic matter. Adding H₂O₂ concentrations below 10^?5M to phosphate buffered solutions has a negligible effect on the ozone decay rate compared with pure water systems, except for pH 7. It appears that phosphate masks the effect of hydrogen peroxide below 10^?5 M as tested here. Thus the application of AOP's by adding low concentrations of hydrogen peroxide is not well feasible in the presence of phosphate buffers in pure water systems.     

Removal of Ethylenediaminetetraacetic acid (EDTA) from Pulp Mill Effluents by Ozonation

Ozone application was investigated for its effectiveness in the removal of ethylenediaminetetraacetic acid (EDTA) from bleaching effluent. The objectives were to compare the efficiency of ozone reaction on Na-EDTA solution with pure Fe³⁺-EDTA complex and EDTA complexes in bleaching effluent, and to test if changing pH and addition of hydrogen peroxide (H₂O₂) increases the removal of EDTA. Small ozone doses destroyed high proportions of Na-EDTA. This effect was diminished when EDTA formed complexes with other metal ions. It was shown that EDTA present in bleaching effluent was more easily oxidizable than in pure Fe³⁺-EDTA solution. Variation of initial pH value had no significant influence on the removal of Na-EDTA. Addition of hydrogen peroxide did not increase degradation of EDTA in bleaching effluent.