Ozone,Hydrogen Peroxide/Ozone And UV/Ozone Treatment Of Chromium- And Copper-Complex Dyes: Decolorization And Metal Release

Metal-complex azo dyes constitute a significant fraction of the dyes used in the textile industry and exhibit properties such as superior light- and wash-fastness. While effluent color is not always regulated, the textile finishing industry often decolorizes wastewater using processes including chemical oxidation. In this study, the use of ozone, hydrogen peroxide/ozone and UV/ozone oxidant systems was examined for treatment of two common metal-complex (premetalized) dyes, Acid Black 52 (chromium) and Direct Blue 80 (copper). Oxidant dosages required for decolorization of these dyes were determined. The effect of bicarbonate alkalinity on the ozonation and the hydrogen peroxide/ozone processes also was examined.     

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 Return of Ozone and the Hydroxyl Radical to Wastewater Disinfection

The City of Phoenix, Arizona is investigating various disinfection technologies for its 91st Avenue wastewater treatment facility: (1) ultraviolet light (UV), (2) ozone, (3) UV/hydrogen peroxide, (4) ozone/hydrogen peroxide, (5) and UV/ozone. In addition to providing disinfection, the City would like to consider the removal of endocrine disrupting chemicals (EDCs) and personal and pharmaceutical care products (PPCPs) in the treatment technology evaluation. To identify the most economical disinfection system, the evaluation included bench-scale testing of the technologies considered and a year-long water quality monitoring study. This paper presents the results of the bench-scale analyses and estimated capital and O&M costs.     

Pilot-Plant-Scale Ozone and PEROXONE Disinfection of Giardia muris Seeded into Surface Water Supplies

PEROXONE is an advanced oxidation process for water treatment which is generated by combining ozone and hydrogen peroxide. In this study, surface water supplies were seeded with viable Giardia muris cysts and disinfected by ozone and PEROXONE in the pretreatment columns of a 22.7 L/min pilot plant. Inactivation was examined in two source waters under conditions of varying applied ozone doses (0.5–4.0 mg/L), with and without the addition of hydrogen peroxide; at increasing contact times (3, 6, 9, and 12 min); and with and without added high turbidity (10 and 50 NTU). Approximately 10⁸ viable G. muris cysts were injected into the ozone contactor-column influent. The cysts were collected at the ozone contactor-column effluent and concentrated, and viability was then determined using in vitro excystation.     

Inactivation of Giardia muris Using Ozone and Ozone-Hydrogen Peroxide

The disinfection effects of the ozone molecule alone and that of ozone decomposition products when inactivating Giardia muris cysts were investigated at bench-scale using two different ozone demand-free laboratory buffer systems. The first water was a 0.05 M phosphate buffer with hydrogen peroxide added at a 10:1 weight ratio. The second water was a 0.05 M phosphate – 0.01 M bicarbonate buffer which quickly scavenged radical species from ozone decomposition. The C3H/HeN mouse model was used to assess the infectivity of ozone treated cysts.

The phosphate-bicarbonate buffer system had significantly greater (P ≤ 0.05) inactivation of G. muris cysts than that observed in the phosphate buffer – peroxide system where ozone was completely decomposed in less than 120 s. Consequently, the design of ozone disinfection processes should maintain ozone residual for disinfection prior to the addition of hydrogen peroxide for the oxidation of other compounds.     

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.     

Impact of Ozone and Hydrogen Peroxide vs. UV and Hydrogen Peroxide on Chlorine Residual

The current study undertaken by the Walkerton Clean Water Centre (WCWC) is to evaluate the application of Advanced Oxidation Processes (AOPs) involving Ozone and UV with the addition of hydrogen peroxide, as one of the methods used in the process of the removal of PPCPs and EDCs, or taste and odor. The amount of hydrogen peroxide used with UV is much higher than that used with the ozone application. The concern is the impact of the hydrogen peroxide on the chlorine residual in the water that is pumped to the distribution system. One of the methods used to deal with this problem is to increase the chlorine addition to maintain the required residual. That could increase the disinfectant by-products (DBPs), namely Trihalomethanes (THMs), in addition to increase to the cost of operation. The findings of these experiments would provide useful information regarding the AOPs application using ozone vs. UV with hydrogen peroxide.     

Bromate Formation in Ozone and Advanced Oxidation Processes

Both the direct ozone reaction and the indirect hydroxyl radical reaction are important in ozonation of drinking water. This article investigates the effectiveness of ozone versus the advanced oxidation process of ozone coupled with hydrogen peroxide in the formation of bromate. The investigation was conducted on a pilot scale at various H₂O₂:O₃ dose ratios of 0.1, 0.2, and 0.35 at different times of the year. The results of this study show a reduction in bromate with the addition of hydrogen peroxide to an ozone system versus ozone alone. It was also observed that bromate increased with increased H₂O₂:O₃ ratios; however, concentrations were still lower than those in the ozone only system.     

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.     

Water Disinfection of Dental Units using Ozone – Microbiological Results after 11 Years and Technical Problems

Water disinfection in dental treatment units using ozone and hydrogen peroxide/silver ion were compared for a period of 11 years. Water from nine treatment units was microbiologically examined in a total of 240 tests. Eight treatment units using peroxide disinfection regularly exceeded the limits stipulated by water purity regulations, and Pseudomonas aeruginosa was detected at 154 water outlets. However, hardly any of the water specimens taken from the treatment unit using ozonated water disinfection showed bacteria. Four technical problems to using ozonated water were found during this eleven year period. The use of hydrogen peroxide necessitated 48 basic disinfections.     

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.     

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.     

Kinetic Study of Ozone Decay in Homogeneous Phosphate-Buffered Medium

The ozone decomposition reaction is analyzed in a homogeneous reactor through in-situ measurement of the ozone depletion. The experiments were carried out at pHs between 1 to 11 in H₂PO₄^?/HPO₄^2– buffers at constant ionic strength (0.1 M) and between 5 and 35 °C. A kinetic model for ozone decomposition is proposed considering the existence of two chemical subsystems, one accounting for direct ozone decomposition leading to hydrogen peroxide and the second one accounting for the reaction between the hydrogen peroxide with the ozone to give different radical species. The model explains the apparent reaction order respect of the ozone for the entire pH interval. The decomposition kinetics at pH 4.5, 6.1, and 9.0 is analyzed at different ionic strength and the results suggest that the phosphate ions do not act as a hydroxyl radical scavenger in the ozone decomposition mechanism.     

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).     

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.     

Production and Removal of Assimilable Organic Carbon Under Pilot-Plant Conditions Through the Use of Ozone and PEROXONE

Pilot-plant studies were conducted in two source waters to determine the effects of predisinfection with ozone alone and with a combination of hydrogen peroxide and ozone (PEROXONE) on the production of assimilable organic carbon (AOC) compounds. Colorado River water (CRW) and State project water (SPW) from Northern California were treated with ozone alone at applied dosages ranging from 1 to 4 mg/L and with PEROXONE at hydrogen peroxide/ozone (H₂O₂/O₃) ratios of 0.05, 0.10, 0.20, and 0.30. Ozonation of CRW with applied dosages of 1.0,2.0, and 4.0 mg/L increased AOC concentrations from 70μg C/L to 275, 350, and 224 μg C/L, respectively. Ozonation of SPW with an applied dosage of 4.0 mg/L elevated AOC concentrations from 70 to 522μg C/L.     

Ozone kinetics and diesel decomposition by ozonation in groundwater

The ozone kinetics (ozone auto-decomposition; effects of pH and solubility) and diesel/TCE/PCE decomposition (effects of hydroxyl radical scavenger, pH, and ozone/H₂O₂) by ozonation process were investigated in aqueous phase using deionized water, simulated groundwater, and actual groundwater. Reactions with deionized water and groundwater both showed the second-order reaction rates: the reaction rate was much higher in groundwater (half-life of 14.7 min) than in deionized water (half-life of 37.5 min). It was accelerated at high pH condition in both waters. The use of ozone showed high oxidation rates of TCE, PCE, and diesel. Hydroxyl radical scavengers acted as inhibitors for diesel decomposition, and high pH condition and addition of hydrogen peroxide could promote to degrade diesel in groundwater indicating ozone oxidation process could be effectively applied to treating diesel contaminated-groundwater.     

Influence of Carbonate on the Ozone/Hydrogen Peroxide Based Advanced Oxidation Process for Drinking Water Treatment

The influence of carbonate on the ozone/hydrogen peroxide process has been investigated. Carbonate radicals, which are formed from the reaction of bicarbonate/carbonate with OH radicals, act as a chain carrier for ozone decomposition due to their reaction with hydrogen peroxide. The efficiency of bicarbonate/carbonate as a promoter for the radical-based chain reaction in presence of hydrogen peroxide has been calibrated and compared to a well-known chain promoter (methanol) and an inhibitor (tert-butanol). Relative to tert-butanol, the hydrogen peroxide induced ozone decomposition is accelerated by bicarbonate/carbonate. Relative to methanol, bicarbonate/carbonate in presence of hydrogen peroxide is less effective as a promoter under comparable experimental conditions.     

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.     

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.