Kinetics of Estrone Ozone/Hydrogen Peroxide Advanced Oxidation Treatment

Ozone/hydrogen peroxide batch treatment was utilized to study the degradation of the steroidal hormone estrone (E1). The competition kinetics method was used to determine the rate constants of reaction for direct ozone and E1, and for hydroxyl radicals and E1 at three pH levels (4, 7, and 8.5), three different molar O₃/H₂O₂ ratios (1:2, 2:1, and 4:1) and a temperature about 20°C. The average second-order rate constants for direct ozone-E1 reaction were determined as 6.2?×?10³?±?3.2?×?10³ M^?1s^?1, 9.4?×?10⁵?±?2.7?×?10⁵ M^?1s^?1, and 2.1?×?10⁷?±?3.1?×?10⁶ M^?1s^?1 at pH 4, 7, and 8.5, respectively. It was found that pH had the greatest influence on the reaction rate, whereas O₃/H₂O₂ ratio was found to be slightly statistically significant. For the hydroxyl radical-E1 reaction, apparent rate constants ranged from 1.1?×?10¹⁰ M^?1s^?1 to 7.0?×?10¹⁰ M^?1s^?1 with an average value of 2.6?×?10¹⁰ M^?1s^?1. Overall, O₃/H₂O₂ is shown to be an effective treatment for E1.     

Decomposition of 2-Chlorophenol in Aqueous Solutions by Ozone and UV/Ozone Processes in the Presence of t-Butanol

The decomposition of 2-chlorophenol in aqueous solutions by ozone and UV/ozone process was studied with the presence of t-butanol. The addition of t-butanol decreased the surface tension of aqueous solutions and subsequently increased the gas-liquid contact area. The presence of t-butanol did not affect the steady-state dissolved ozone concentration in aqueous solution; however, the ozone transfer rate between gas-liquid interface was noticeably enhanced and the time required to reach the steady state was reduced. The presence of t-butanol was found to promote the decomposition of 2-chlorophenol for both ozone and UV/ozone processes. Nonetheless, the presence of excessive dosages of t-butanol might decrease the reaction rates for experiments conducted in alkaline solutions probably because t-butanol also served as the scavenger for hydroxyl free radicals.     

Influence of Liquid Height to the Oxidation Process of Landfill Leachate by Using Ozone

The influence of liquid height on chemical oxygen demand (COD) of leachate was investigated. When 400 mL leachate was filled in a thick tube reactor (TTR) with height of 0.063 m, COD removal efficiency was 45.69%, while ozone dosage was 3.35 mg_O3/mg_COD. As leachate was filled in a slender tube reactor (STR) with a height of 0.815 m, removal efficiency was 51.81%, and ozone dosage was 3.12 mg_O3/mg_COD. The results indicated that COD removal efficiency increased with the height of liquid. It is believed that the liquid height increased hydraulic pressure and resulted in COD removal efficiency.     

Performance and Mechanism on Degradation of Estriol Using O3/PS Process

In this study, enhanced ozonation of estriol (E3) with persulfate (PS) was investigated in aqueous solution. Simultaneous generation of hydroxyl radical (?OH) and sulfate radical (?SO₄^?) by O₃/PS process was proposed and experimentally verified. Kinetic results revealed that the degradation of E3 was affected by the solution pH, PS concentration, O₃ dosage and E3 initial concentration. The optimal reaction rate was observed in alkaline solutions. The mechanism for the synergistic effect was preliminarily explored by the addition of hydroxyl and sulfate radical scavengers. The enhanced degradation of E3 by O₃/PS was also observed in actual water samples, which provided impetus for practical applications. The degradation intermediates were detected using LC/MS. Results showed that the phenol structures of the estrogens were mostly oxidized to cyclohexenone moieties and quinone-like structures.     

Degradation of Recalcitrant Surfactants in Wastewater by Ozonation and Advanced Oxidation Processes: A Review

Surfactants are used in varieties of industrial cleansing processes as well as in consumer products. Spent surfactants normally enter domestic or industrial wastewater and are treated biologically. However, some of them are resistant to biodegradation and are released into the environment. Thus, the toxicity and environmental persistence of these surfactants are emerging concerns. Based on extensive review of the literature, ozonation and advanced oxidation using various combinations of ozone, hydrogen peroxide, ultraviolet light irradiation, and iron salts were found effective in degrading recalcitrant surfactants, including linear alkylbenzene sulfonates, alkylphenol ethoxylates, and quaternary ammonium surfactants. Biodegradability of these surfactants was improved after the treatment to some extent in the aqueous solution as well as in real wastewaters.     

Degradation of Caffeine by Advanced Oxidative Processes: O3 and O3/UV

The degradation of caffeine by ozone was investigated in this article. In the laboratory experimental scale, the effect of pH, caffeine initial concentration, power UV light and reaction time were studied by experimental design. The use of response surface methodology (RSM) allowed to adjust the optimal regions of the parameters leading to the response factor (% mineralization). In addition, a single polynomial expression for modeling the reaction was obtained. Results clearly demonstrated that caffeine is quickly degraded, but not mineralized as quickly. The results indicated that the caffeine mineralization rate increased with pH and reaction time. Power UV light showed little effect on mineralization efficiency.     

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).     

Degradation of Refractory Organic Pollutants by Catalytic Ozonation—Activated Carbon and Mn-Loaded Activated Carbon as Catalysts

A novel catalyst for the ozonation process was prepared by loading manganese on the granular activated carbon (GAC). Nitrobenzene was used as a model refractory organic micropollutant in this study. The catalytic activity of GAC and the Mn-loaded GAC were studied respectively. The removal efficiency of nitrobenzene by Mn-loaded GAC catalyzed ozonation could reach 34.2–49.9%, with the oxidation efficiency being about 1.5–2.0 times higher than that achieved in GAC catalyzed ozonation and 2.0–3.0 times higher than that achieved by ozonation alone. The effect of pH and the t -butanol on the GAC/ozone process was discussed. The optimum condition for preparing the catalyst was studied.     

Degradation of Aqueous Pharmaceuticals by Ozonation and Advanced Oxidation Processes: A Review

A vast number of pharmaceuticals have been detected in surface water and drinking water around the world, which indicates their ineffective removal from water and wastewater using conventional treatment technologies. Concerns have been raised over the potential adverse effects of pharmaceuticals on public health and aquatic environment. Among the different treatment options, ozonation and advanced oxidation processes are likely promising for efficient degradation of pharmaceuticals in water and wastewater. Recent progress of advanced oxidation of aqueous pharmaceuticals is reviewed in this paper. The pharmaceuticals and non-therapeutic medical agent of interest include antibiotics, anticonvulsants, antipyretics, beta-blockers, cytostatic drugs, H₂ antagonists, estrogenic hormone and contraceptives, blood lipid regulators, and X-ray contrast media.     

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.