The role of hydroxyl radical reactions in ozonation processes in aqueous solutions

Hydroxyl radicals are formed upon the hydroxide-ion catalyzed decomposition of ozone in water as is shown by the relative rates with which organic substrates compete with each other for consuming the oxidative intermediates. The yield of the decarboxylation of ¹⁴C-labelled benzoic acid indicates that up to 0.55 ± 0.08 mol of hydroxyl radicals may be produced from 1 mol ozone at pH 10.5. Published data on hydroxyl radical-reactions can now be applied to describe oxidations initiated by ozonation. Parameters influencing the prior ozone decomposition and protective effects of radical scavengers, such as carbonates, have to be accounted for when optimizing the processes. The solutes present in water influence appreciably the rate of the chain reaction leading to the decomposition of ozone.     

A comparison of fenuron degradation by hydroxyl and carbonate radicals in aqueous solution

A comparative study of the transformation of the herbicide fenuron (1,1-dimethyl-3-phenylurea) by hydroxyl radicals and carbonate radicals in aqueous solution (pH 7.2-phosphate buffer) has been undertaken. Hydroxyl radical was generated by the well-known photolysis of hydrogen peroxide at 254 nm and carbonate radical was formed by photolysis of Co(NH₃)₅CO₃⁺ at 254 nm. Competitive kinetic experiments were performed with atrazine used as the main competitor for both processes. Accordingly, the second-order rate constant of reaction between fenuron and carbonate radical was found to be (7−12±3)×10⁶ M⁻¹ s⁻¹ [(7±1)×10⁹ M⁻¹ s⁻¹ for hydroxyl radical]. The formation of degradation products was studied by LC-MS in the two cases and a comparison has been performed. The reaction with carbonate radical leads to the formation of a quinone-imine derivative which appears as the major primary product together with ortho and para hydroxylated compounds. These two compounds represent the major products in the reaction with hydroxyl radicals. The reaction of both radicals also leads to the transformation of the dimethylurea moiety.     

Protocatechuic acid ozonation in aqueous solutions

The oxidation of protocatechuic acid with ozone in aqueous solution has been studied varying the temperature, pH, ozone partial pressure and initial acid concentration. A stoichiometric ratio of 2 mol of ozone consumed per mol of protocatechuic acid reacted is deduced from homogeneous experiments in a discontinuous tank reactor.In the ozonation experiments, the influence of the operating variables was established and the kinetic regime of ozone absorption was shown to be fast and pseudo m-order with respect to ozone, except at pH 2, when the reaction develops in the moderate kinetic regime. After applying a mass transfer with chemical reaction model, the reaction orders are deduced and the kinetic rate constants are determined as a function of pH and temperature. A modified Arrhenius expression is proposed to correlate them.     

Degradation of atrazine in aqueous medium by electrocatalytically generated hydroxyl radicals. A kinetic and mechanistic study

Oxidative degradation of atrazine by hydroxyl radicals (OH) was studied in aqueous medium. OH were formed in situ from electrochemically generating Fenton's reagent by an indirect electrochemical advanced oxidation process. Identification and evolution of seven main aromatic metabolites and four short-chain carboxylic acids were performed by using liquid chromatography analyses. Total organic carbon (TOC) and ionic chromatography were used in order to evaluate the mineralization efficiency of treated aqueous solutions. A high mineralization rate of 82% (never reported until now) was obtained. The oxidative degradation of cyanuric acid, the ultimate product of atrazine degradation, was highlighted for the first time. The absolute rate constant of the reaction between atrazine and hydroxyl radicals was evaluated by competition kinetics method as (2.54 ± 0.22) × 10⁹ M⁻¹ s⁻¹. Considering all oxidation reaction intermediates and end products a general reaction sequence for atrazine degradation by hydroxyl radicals was proposed.     

The role of nitrobenzene on the yield of trihalomethane formation potential in aqueous solutions with Microcystis aeruginosa

Algae are one of the most important disinfection by-product (DBP) precursors in aquatic environments. The contents of DBP precursors in algae are influenced by not only environmental factors but also some xenobiotics. Trihalomethane formation potential (THMFP) in both the separate and interactive pollution of Microcystis aeruginosa and Nitrobenzene (NB) was investigated in batch experiment to discover the effects of xenobiotics on the yield of DBP precursors in the algal solution. The results show that in the separate NB solution, NB did not react with Cl₂ to form trihalomethane (THM), whereas in the algae solution, THMFP had a significant positive linear correlation with M. aeruginosa density in both solution and extracellular organic matter (EOM). The correlation coefficients were 0.9845 (p = 3.567 × 10⁻⁴) and 0.9854 (p = 1.406 × 10⁻⁴), respectively. According to regression results, about 77.9% of the total THMFP came from the algal cells, while the rest came from EOM. When the interactive pollution of M. aeruginosa and NB occurred, the growth of algae was inhibited by NB. The density of M. aeruginosa in a high concentration NB solution (280 μg/L) was only 71.1% of that in the solution without NB after 5 days of incubation. However, THMFP in the mixture (algae and NB) and the EOM did not change significantly, and the productivity of THMFP by the algae (THMFP/10⁸cells) increased with the increase in NB concentration. There was a significant linear correlation between THMFP/10⁸cell and NB concentration (r = 0.9117, p < 0.01), which shows the contribution of the algae to THM formation was enhanced by NB. This result might be caused by the increased protein productivity and the biodegradation of NB by M. aeruginosa.     

Intensification of the ultrafiltration process when separating aqueous solutions of acid dyes

We have investigated the impact of working pressure, the degree of sampling permeate, the pH of the medium on the transmembrane flow and retention capacity of a UPM-50 ultrafiltration membrane with respect to the dye acid yellow in the combination of the method of ultrafiltration and coagulation. It has been shown that the use of magnesium hydroxide for aggregation of anionic dyes makes it possible to substantially increase the efficiency of their membrane removal from the solution retaining high capacity of the ultrafiltration process.     

Degradation of monomethylmercury chloride by hydroxyl radicals in simulated natural waters

The degradation of methylmercury chloride by hydroxyl radicals (*OH) has been investigated using nitrate photolysis from 285 to 800 nm with a 450 W Xenon lamp as the (*OH source. The identified products are Hg(2+), Hg(0), CHCl(3) and formaldehyde. The second-order rate constant at pH of 5 at room temperature was determined to be 9.83(+-0.66)x10(9) M(-1) x s(-1)using benzoic acid as the *OH scavenger. The effects of chloride concentration and methylmercury speciation have also been investigated. A mechanism of the CH(3)HgCl-*OH reaction has been proposed. The calculated methylmercury degradation rates in natural waters using the above rate constant were comparable to the in situ photodegradation rates reported previously, indicating that degradation by (*)OH may be one of the important pathways of methylmercury degradation in sunlit surface waters.     

The kinetics of ozone-phenol reaction in aqueous solutions

The kinetics of the reaction of ozone and phenol in aqueous medium was studied. The reaction was first order with respect to both ozone and phenol. The rate constant was found to increase with increase in the pH of the reaction mixture. Four different catalysts were examined for their effect on the rate of reaction but none of them was found to have any appreciable effect. The presence of additional solutes like sodium chloride, sodium carbonate and sodium sulfate was found to affect the reaction significantly. The experiments indicated that hydroxyl radicals may not play a role in the attack of ozone on phenol and the reaction mechanism may be ionic rather than free radical.     

The degradation products of UV filters in aqueous and chlorinated aqueous solutions

Ultraviolet (UV) filters are vital constituents of sunscreens and other personal care products since they absorb, reflect and/or scatter UV radiation, therefore protecting us from the sun’s deleterious UV radiation and its effects. However, they suffer degradation, mainly through exposure towards sunlight and from reactions with disinfectant products such as chlorine. On the basis of their increasing production and use, UV filters and their degradation products have already been detected in the aquatic environment, especially in bathing waters. This paper presents a comprehensive review on the work done so far as to identify and determine the by-products of UV filter photodegradation in aqueous solutions and those subsequent to disinfection-induced degradation in chlorinated aqueous solutions, namely swimming pools.     

Sonochemical decomposition of dibenzothiophene in aqueous solution

Dibenzothiophene is decomposed rapidly by sonication in aqueous solution. Decomposition of dibenzothiophene follows a first-order reaction kinetics. The rate constant was found to increase with increasing ultrasonic energy intensity, temperature, and pH and decrease with increasing initial dibenzothiophene concentration. The activation energy was 12.6 kJ/mol in the temperature range of 15–50°C, suggesting a diffusion-controlled reaction. Hydroxydibenzothiophenes and dihydroxydibenzothiophenes were identified as reaction intermediates. It is proposed that dibenzothiophene is oxidized by OH radical to hydroxy-dibenzothiophenes and then to dihydroxy-dibenzothiophenes. Kinetic analysis suggests that approximately 72% of the dibenzothiophene decomposition occurred via OH radical addition. A pathway and a kinetic model for the sonochemical decomposition of dibenzothiophene in aqueous solution are proposed.     

Model studies in aqueous chlorination: The chlorination of phenols in dilute aqueous solutions

A study of the chlorination of four phenols in dilute aqueous solution at initial pH's of 6.0 and 3.5 is described. Extensive chlorination is observed under these mild reaction conditions. Identification of the products indicates that the reactions occurring involve chlorination to more highly chlorinated phenols, oxidation to chlorinated p-benzoquinones, chlorine addition to the aromatic ring to form chlorinated 2,5-cyclohexadienones, and addition of 2 moles of chlorine or one each of chlorine and hypochlorous acid to give chlorinated cyclohexenones and chlorinated hydroxycyclohexenones.     

Spectrophotometric method for determination of ozone in aqueous solutions

A sensitive spectrophotometric method for determination of ozone in small volumes of water is presented. It was performed in order to meet the requirements of a kinetic study of virus and bacteria inactivation by ozone.The proposed method involves oxidation of a buffered iodine solution and spectrophotometric measurement of the triiodide ion liberated by ozone. Two procedures are used: one for low ozone concentration (0·01–0·30 ppm) and another for higher concentrations (0·30–2·0 ppm). The reproducibility of results is very high when the procedure used corresponds with the ozone level for which it is intended.This spectrophotometric method is compared with the standard volumetric method and the differences are presented and discussed.Some applications of the method for a kinetic study of virus inactivation by ozone are presented.     

Direct photolysis of estrogens in aqueous solutions

Direct photolysis of two estrogens 17beta-estradiol (E2) and estrone (E1) in aqueous solutions radiated by UV-light and UV-Vis-light was studied preliminarily. The results suggest that the photolysis of E2 in aqueous solutions occurs under irradiation with UV disinfection lamp (lambda = 254 nm, 30 W), while E1 can also undergo photolysis under irradiation with a high-pressure mercury lamp (lambda > or = 365 nm, 125 W). The photolysis reactions of E2 and E1 at the concentration of 3.0-20 mgl(-1) in aqueous solutions were all in accordance with pseudo-first-order law. The photolysis rate of estrogens in aqueous solutions reached the lowest value at pH approximately 5.0, while the highest at pH 8.0 over the range of 2.0-8.0. The higher the initial concentration of the two estrogens, the lower the rate of photolysis.     

Space decomposition based parallelization solutions for the combined finiteediscrete element method in 2D

The combined finiteediscrete element method （FDEM） belongs to a family of methods of computationalmechanics of discontinua. The method is suitable for problems of discontinua, where particles aredeformable and can fracture or fragment. The applications of FDEM have spread over a number of disciplinesincluding rock mechanics, where problems like mining, mineral processing or rock blasting canbe solved by employing FDEM. In this work, a novel approach for the parallelization of two-dimensional（2D） FDEM aiming at clusters and desktop computers is developed. Dynamic domain decompositionbased parallelization solvers covering all aspects of FDEM have been developed. These have beenimplemented into the open source Y2D software package and have been tested on a PC cluster. Theoverall performance and scalability of the parallel code have been studied using numerical examples. Theresults obtained confirm the suitability of the parallel implementation for solving large scale problems.
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Radiation-induced degradation of polyvinyl alcohol in aqueous solutions

The degradation of polyvinyl alcohol (PVA) by gamma-ray irradiation was investigated. Degradation efficiency of PVA was influenced by several factors, such as initial PVA concentration, dose rate, pH, and the addition of H2O2. The degradation kinetics depended on initial PVA concentration and dose rate. At a relatively lower PVA concentration, e.g., 180 mg/L, and a higher dose rate, e.g., 55.7 Gy/min, the degradation followed pseudo-first-order kinetics. On the contrary, at a higher PVA concentration, e.g., 500 mg/L, but a lower dose rate, e.g., 12.1 Gy/min, a pseudo-zero-order reaction occurred. The removal of PVA was more effective under acidic or alkaline conditions than that under neutral conditions. At a certain dose rate there was an optimal dosage of H2O2 to facilitate the degradation of PVA. For instance, at a dose rate of 17.2 Gy/min, the optimal H2O2 dosage was found to be about 2.5 mmol/L. Radical scavenging experiments, total organic carbon determination, and FTIR analysis on the degradation products demonstrated that PVA radiolysis was initiated by *OH and H*, leading to chain scission and formation of ketones/enols. Ultimately, complete mineralization of PVA was achieved.     

The reaction of nucleotides with aqueous hypochlorous acid

It has been found that the rate of consumption of hypochlorous acid by the nucleotides cytidine monophosphate (CMP) and adenosine monophosphate (AMP) increases with decreasing pH. At pH 5.6, CMP and AMP are the primary consumers of free chlorine; at pH 7.6 guanosine monophosphate (GMP), as well as CMP and AMP, react readily with hypochlorous acid. At pH 10, the only consumer of hypochlorite is GMP. A parallel was found between the rate of inactivation of virus and the rate of consumption of free chlorine by two of the nucleotides; both the rate of virus inactivation and the rate of consumption of chlorine by AMP and CMP increase with decreasing pH. Under conditions of virus disinfection, uridine monophosphate (UMP) is quite unreactive with aqueous hypochlorous acid.     

The adsorption of nicotine from aqueous solutions on different zeolite structures

The present work is focused on the adsorption of nicotine from aqueous solutions. Based on the data available in the literature, serious concern is claimed regarding the appearance of nicotine in ground, surface and municipal wastewaters. In order to investigate the possibility of abatement by adsorption, three different types of zeolites (BEA, MFI and HEU) have been applied as adsorbents. In addition, the adsorption was performed on activated carbon, a solid customarily used for removal of pollutants from water. The adsorption of nicotine was studied by isothermal microcalorimetry, which provided the heats evolved as a result of adsorption. The values of these heats revealed that the investigated solids are energetically heterogeneous for the adsorption of nicotine from aqueous solution. Additionally, the amounts of adsorbed pollutant were determined and presented in the form of adsorption isotherms. The obtained adsorption isotherms were interpreted using Langmuir, Freundlich, and Sips equations; the latter was found to express high level of agreement with experimental data of nicotine adsorption on the investigated solids. The possibilities to regenerate the adsorbents were examined by means of thermogravimetry coupled with mass spectrometry. From all obtained results, it was possible to distinguish zeolite BEA as a material which possesses the capacity for adsorption of nicotine comparable to that of activated carbon.