Selection of supported cobalt substrates in the presence of oxone for the oxidation of monuron.

The immobilization of cobalt ion on different media to catalyze oxone has been investigated. A probe herbicide, Monuron, was effectively degraded by using Co2+/oxone systems. For Co2+ supported on zeolite, 100% of Monuron could be removed within a 10 min reaction time. However, the recycling of the spent Co-zeolite catalyst using various posttreatments did not give a promising result. This is likely because the zeolite particles in solution have blocked and significantly attenuated the incident UV light from reducing Co3+ to Co2+. On the contrary, the use of cationic resin has minimized these problems. In the process of Co-resin/oxone/UV, faster Monuron decay could be achieved than that in the dark reaction. In the presence of UV, a significant drop of total organic carbon (TOC) was also observed in this approach suggesting an effective and clean process for Monuron mineralization.

The effect of solution pH and peroxide in the TiO2-induced photocatalysis of chlorinated aniline.

Chlorinated anilines are frequently used in the industry as starting materials for chemical synthesis. This type of compounds can end up as pollutants in wastewater. 2-Chloroaniline (2-ClA) was selected irradiating under monochromatic UV light at 300nm. The reaction rate could be enhanced by introducing low level of H(2)O(2) into the UV/TiO(2) system. Excess H(2)O(2) could not increase the HO* generation but retarded the reaction rate. The pH effect was also investigated in UV/TiO(2) and UV/TiO(2)/H(2)O(2) systems. All the experimental results show that pH is a sensitive parameter to the rate of degradation. Low reaction rate at acidic pH could be accounted by the dark adsorption test which has also proven the photocatalysis of TiO(2) may contribute to a two-step process: (1) 2-ClA pre-adsorbed onto TiO(2) and (2) photoexcitation of TiO(2). At high pH, rate enhancement could be observed at UV/TiO(2) system because of the increase generation of HO*. However, the introduction of H(2)O(2) slowdown the decay rate at such alkaline medium.

The use of oxyhalogen in photocatalytic reaction to remove o-chloroaniline in TiO2 dispersion.

Photodecay of o-chloroaniline (o-ClA) in various combinations of UV sources, TiO2, and oxyhalogens was investigated. To improve the conventional photocatalytic process by using UV/TiO2, the addition of oxyhalogens (ClO3(-), BrO3(-) and IO3(-)) into UV/TiO2 system was studied and the effect in such addition is very encouraging for all the selected additives. Oxyhalogens are capable of deferring the electron-hole recombination of TiO2 which significantly improved its catalytic performance. The presence of IO3(-) in UV/TiO2 resulted in the fastest o-ClA decay among three oxhalogens at the same dosage. The decay of o-ClA in UV/TiO2/oxyhalogen process is characterized by a two-stage pseudo-kinetics, where a faster initial decay was followed by a retardation state. A mathematics model was successfully established for the prediction of the two-stage decay of o-ClA in UV/TiO2/IO3(-) with any designed [IO3(-)] concentration.

The partitioning and modelling of pesticide parathion in a surfactant-assisted soil-washing system.

Soil sorption of organic pollutants has long been a problematic in the soil washing process because of its durability and low water solubility. This paper discussed the soil washing phenomena over a wide range of parathion concentrations and several soil samples at various fractions of organic content (foc) levels. When parathion dosage is set below the water solubility, washing performance is stable for surfactant concentrations above critical micelle concentration (cmc) and it is observed that more than 90% of parathion can be washed out when dosage is five times lower than the solubility limit. However, such trends change when non-aqueous phase liquids (NAPL) is present in the system. Parathion extraction depends very much on the surfactant dosage but is not affected by the levels of foc in the system. In between the extreme parathion dosage, a two-stage pattern is observed in these boundary regions. Washing performance is first increased with additional surfactant, but the increase slows down gradually since the sorption sites are believed to be saturated by the huge amount of surfactant in the system. A mathematical model has included foc to demonstrate such behavior and this can be used as a prediction for extraction.

Effects of nonaqueous phase liquids on the washing of soil in the presence of nonionic surfactants.

The removal of malathion from soil by surfactant washing was investigated under various physical-chemical states of the malathion. Three distinctive phases (without nonaqueous phase liquids (NAPL), with NAPL, and the transitional zone of NAPL) were found to be important for a better understanding of the washing process. When there is no NAPL in the system, the washing process is less dependent on the surfactant dose if the applied surfactant concentration is above the critical micelle concentration. The existence of a sorption site boundary, which for the determination of different washing mechanisms, was identified. In the presence of NAPL, the washing performance is generally independent of the organic content (f(oc)) of the soils but is dominated by the concentration of the surfactant used, due to the lesser resistance for mass transfer in NAPL. If the formation of NAPL is marginal, a two-stage washing pattern is observed, which has been quantified by the term 'unit extraction'. For this two-stage system, a mathematical model was derived based on the observed initial unit extraction and final extraction capacity, which eventually resulted in a practical design equation with the use of primary parameters such as f(oc) and surfactant dose.

The mechanisms of rate enhancing and quenching of trichloroethene photodecay in the presence of sensitizer and hydrogen sources.

The reaction mechanisms and rates of trichloroethene (TCE) photodecay in the presence of photosensitizer (acetone, ACE) and hydrogen sources (surfactant and triethylamine, TEA) were investigated. Quantum yields of TCE photodecay in solution with surfactant Brij 35 and optimal ACE dosage are about 25 times higher than in Brij 35 alone. However, with an excess ACE dosage, ACE will act as a light barrier and attenuate the light intensity available for TCE photodegradation. TCE photodegradation follows a two-stage kinetics, in which a lag-phase is followed by a fast decay. The lag-phase distribution depends on initial pH levels and ACE concentrations. The overall TCE removal was found to be higher at high pH level, suggesting that free radical reaction is dominant at high pH levels. The use of additional hydrogen source (TEA) in the reaction can further accelerate the reaction, but overdosing of TEA would quench the reaction. The possible reaction mechanisms of TCE photodecay involving ACE and TEA were proposed, and rateenhancing and rate-quenching models at low and high TEA concentrations respectively were derived based on the proposed mechanism, they were found useful for predicting the TEC decay quantum yields.

The study of rate improvement of trichloroethene (TCE) decay in UV system with hydrogen source.

The photosensitization of trichloroethene (TCE) in the presence of hydrogen source of surfactant and photosensitizer was investigated. Photolysis experiments were conducted with a Rayonet RPR-200 merry-go-round photoreactor at 253.7 nm. Solutions containing fixed amount of TCE and surfactant Brij 35 were exposed to UV illumination with different concentrations of acetone (ACE). Quantum yield in solution with surfactant Brij 35 and optimum ACE dosage is about 25 times higher than that in Brij 35 alone. However, with an excess ACE dosage, it would act as a light barrier which attenuates the light intensity for TCE photodegradation. A mathematical model is therefore developed for the prediction of TCE photodegradation in Brij 35 solution containing various ACE concentrations, in which the remaining fraction of TCE (C/C0) in the system can be determined. Apart from the direct photodegradation, photosensitization is postulated to be another major pathway contributing to the overall decay.

The rate improvement and modeling of trichloroethene photodegradation by acetone sensitizer in surfactant solution.

The photodecay of trichloroethene (TCE) in surfactant solution by the help of photosensitizer (acetone, ACE) was investigated and modeled. Apart from the direct photodegradation, photosensitization is presumed to be one of the major mechanisms contributing to overall decay. Quantum yields of TCE photodecay in solution with surfactant Brij 35 and optimal ACE dosage are about 25 times higher than in Brij 35 alone. However, with an excess ACE dosage, ACE will act as a light barrier and attenuate the light intensity available for TCE photodegradation. TCE photodegradation follows a two-stage kinetics, in which a lag phase is followed by a fast decay. Mathematical models were developed for the prediction of the two-stage photodegradation, in which the remaining fraction of TCE (C/C0) in the system becomes predictable.

The modelling of trichloroethene photodegradation in Brij 35 surfactant by two-stage reaction.

Various clean-up technologies have been developed for the removal and/or destruction of trichloroethene (TCE) in the subsurface. Surfactant-aided soil washing followed by photodegradation could be a promising approach to such a task. The modelling of TCE photodegradation by UV in Brij 35 surfactant micelles is therefore investigated. Two stages of TCE degradation are observed in surfactant Brij 35 systems. A lag phase is observed at the commencement of the degradation, but the duration of the lag phase is significantly reduced as the initial pH increases. As the overall decay of TCE is also found to be faster at higher pH levels, it is suggested that the free radical reaction is dominant at high pH levels, and the formation of lag phases is mainly due to the deficiency of free radicals at lower pH levels. Since the period of the lag phase gradually decreases with the increase of initial pH level, and the two pseudo first-order reaction constants (one for the lag phase and one for the subsequent fast decay) for TCE decay in both stages are also pH dependent, a non-steady-state mathematical model is developed for the prediction of TCE photodegradation in Brij 35 solutions, in which the remaining fraction of TCE (C/C0) in the system can be determined at any instant by using a simple parameter of the initial system pH.

The study of lag phase and rate improvement of TCE decay in UV/surfactant systems.

The photodegradation of trichloroethene (TCE) in surfactant micelles was investigated. The decay of TCE was studied in the Rayonet RPR-200 merry-go-round photoreactor, at 253.7 nm monochromatic ultraviolet (UV) lamps, in the presence of surfactants. Surfactants are used as additional hydrogen sources to improve the photodegradation rates of TCE. About three times the rate increment is observed in the presence of Brij 35 surfactant micelles than in water alone. The increasing concentrations of H+ and Cl- indicate that they are the final products of TCE photodegradation (i.e. photodechlorination is the dominant mechanism in this system). A lag phase is observed at the beginning of the degradation, but the duration of the lag phase is apparently reduced as the initial pH increases. Because the overall decay of TCE is also found faster at higher pH levels, it is suggested that the free radical reaction is dominant at high pH levels, and the formation of lag phases is mainly due to the deficiency of free radicals at lower pH levels. The photodecomposition of TCE in surfactant micelles is also proven to be a clean and effective process. It generates no chlorinated by-products or intermediates during the process, and TCE is fully decomposed within a reasonable time.