Fu-Xiang Tian

Kinetic models and pathways of ronidazole degradation by chlorination, UV irradiation and UV/chlorine processes

Degradation kinetics and pathways of ronidazole (RNZ) by chlorination (Cl2), UV irradiation and combined UV/chlorine processes were investigated in this paper. The degradation kinetics of RNZ chlorination followed a second-order behavior with the rate constants calculated as (2.13 ± 0.15) × 10(2) M(-2) s(-1), (0.82 ± 0.52) × 10(-2) M(-1) s(-1) and (2.06 ± 0.09) × 10(-1) M(-1) s(-1) for the acid-catalyzed reaction, as well as the reactions of RNZ with HOCl and OCl(-), respectively. Although UV irradiation degraded RNZ more effectively than chlorination did, very low quantum yield of RNZ at 254 nm was obtained as 1.02 × 10(-3) mol E(-1). RNZ could be efficiently degraded and mineralized in the UV/chlorine process due to the generation of hydroxyl radicals. The second-order rate constant between RNZ and hydroxyl radical was determined as (2.92 ± 0.05) × 10(9) M(-1) s(-1). The degradation intermediates of RNZ during the three processes were identified with Ultra Performance Liquid Chromatography - Electrospray Ionization - mass spectrometry and the degradation pathways were then proposed. Moreover, the variation of chloropicrin (TCNM) and chloroform (CF) formation after the three processes were further evaluated. Enhanced formation of CF and TCNM precursors during UV/chlorine process deserves extensive attention in drinking water treatment.

Measurement of dissolved organic nitrogen in a drinking water treatment plant: Size fraction, fate, and relation to water quality parameters

This paper investigates the characteristics of dissolved organic nitrogen (DON) in raw water from the Huangpu River and also in water undergoing treatment in the full-scale Yangshupu drinking water treatment plant (YDWTP) in Shanghai, China. The average DON concentration of the raw water was 0.34 mg/L, which comprised a relatively small portion (~5%) of the mass of total dissolved nitrogen (TDN). The molecular weight (MW) distribution of dissolved organic matter (DOM) was divided into five groups: >30, 10-30, 3-10, 1-3 and <1 kDa using a series of ultrafiltration membranes. Dissolved organic carbon (DOC), UV absorbance at wavelength of 254 nm (UV254) and DON of each MW fraction were analyzed. DON showed a similar fraction distribution as DOC and UV254. The <1 kDa fraction dominated the composition of DON, DOC and UV254 as well as the major N-nitrosodimethylamine formation potential (NDMAFP) in the raw water. However, this DON fraction cannot be effectively removed in the treatment line at the YDWTP including pre-ozonation, clarification and sand filtration processes. The results from linear regression analysis showed that DON is moderately correlated to DOC, UV254 and trihalomethane formation potential (FP), and strongly correlated to haloacetic acids FP and NDMAFP. Therefore, DON could serve as a surrogate parameter to evaluate the reactivity of DOM and disinfection by-products FP.

Chlorination of chlortoluron: Kinetics, pathways and chloroform formation

Chlortoluron chlorination is studied in the pH range of 3-10 at 25 ± 1°C. The chlorination kinetics can be well described by a second-order kinetics model, first-order in chlorine and first-order in chlortoluron. The apparent rate constants were determined and found to be minimum at pH 6, maximum at pH 3 and medium at alkaline conditions. The rate constant of each predominant elementary reactions (i.e., the acid-catalyzed reaction of chlortoluron with HOCl, the reaction of chlortoluron with HOCl and the reaction of chlortoluron with OCl(-)) was calculated as 3.12 (± 0.10)×10(7)M(-2)h(-1), 3.11 (±0.39)×10(2)M(-1)h(-1) and 3.06 (±0.47)×10(3)M(-1)h(-1), respectively. The main chlortoluron chlorination by-products were identified by gas chromatography-mass spectrometry (GC-MS) with purge-and-trap pretreatment, ultra-performance liquid chromatography-electrospray ionization-MS and GC-electron capture detector. Six volatile disinfection by-products were identified including chloroform (CF), dichloroacetonitrile, 1,1-dichloropropanone, 1,1,1-trichloropropanone, dichloronitromethane and trichloronitromethane. Degradation pathways of chlortoluron chlorination were then proposed. High concentrations of CF were generated during chlortoluron chlorination, with maximum CF yield at circumneutral pH range in solution.

Degradation kinetics and chloropicrin formation during aqueous chlorination of dinoseb.

The kinetics of chlorination of dinoseb and the corresponding formation of disinfection by-products (DBPs) were studied between pH 4 and 9 at room temperature (25±1°C). The reactivity shows a minimum at pH 9, a maximum at pH 4 and a medium at neutral conditions. pH profile of the apparent second-order rate constant of the reaction of dinoseb with chlorine was modeled considering the elementary reactions of HOCl with dinoseb species and an acid-catalyzed reaction. The predominant reactions at near neutral pH were the reactions of HOCl with the two species of dinoseb. The rate constants of 2.0 (±0.8)×10(4)M(-2)s(-1), 3.3 (±0.6) and 0.5 (±0.1)M(-1)s(-1) were determined for the acid-catalyzed reaction, HOCl reacted with dinoseb and dinoseb(-), respectively. The main degradation by-products of the dinoseb formed during chlorination have been separated and identified by GC-MS with liquid-liquid extraction sample pretreatment. Six volatile and semi-volatile DBPs were identified in the chlorination products, including chloroform (CF), monochloroacetone, chloropicrin (TCNM), 1,1-dichloro-2-methy-butane, 1,2-dichloro-2-methy-butane, 1-chloro-3-methy-pentanone. A proposed degradation pathway of dinoseb during chlorination was then given. TCNM and CF formation potential during chlorination of dinoseb reached as high as 0.077 and 0.097μMμM(-1) dinoseb under the traditional condition (pH=7 and Cl2/C=2). Their yields varied with Cl2/C, pH and time. The maximum yields of TCNM appeared at molar ratio as Cl2/C=1 and pH 3, while the maximum of CF appeared at molar ratio as Cl2/C=4 and pH 7. [TCNM]/[CF] decreased with reaction time and increased solution pH.

Effect of pipe corrosion product–goethite–on the formation of disinfection by-products during chlorination

AbstractThe effect of goethite on the formation of disinfection by-products (DBPs) during chlorination was investigated under various reaction times, pH, and chlorine concentrations. The experimental results indicated that in the presence of goethite, the formation of DBPs was enhanced as pH and chlorine concentration increased. The enhancement of DBP formation could be attributed to the generation of hydroxyl radical (), which could oxidize natural organic matter (NOM) in water and produce more DBP precursors to react with chlorine. X-ray diffraction (XRD) and scanning electron microscope (SEM) analyses of goethite revealed that goethite may adsorb NOM on its surface and modify NOM structure. The reaction mechanisms of goethite-enhanced DBP formation were proposed in three steps: (1) the oxidation of NOM into small molecules available as DBP precursors by from the reaction between ferrous ions on goethite surface and chlorine; (2) the adsorption and modification of NOM on goethite surface responsible for...

Effect of UV irradiation on the proportion of organic chloramines in total chlorine in subsequent chlorination

This study investigated the changes of chlorine species and proportion of organic chloramines during the chlorination process after UV irradiation pretreatment in drinking water. It was found that the UV pretreatment could enhance the percentage of organic chloramines by increasing free chlorine consumption in the chlorination of raw waters. The percentage of organic chloramines in total chlorine increased with UV intensity and irradiation time in raw waters. However, for the humic acid synthesized water, the percentage of organic chloramines increased first and then decreased with the increase of UV irradiation time. The value of SUVA declined in both raw and humic acid synthesized waters over the UV irradiation time, which indicated that the decomposition of aromatic organic matter by UV could be a contributor to the increase of free chlorine consumption and organic chloramine proportion. The percentage of organic chloramines during chlorination of raw waters after 30-min UV irradiation pretreatment varied from 20.2% to 41.8%. Total chlorine decreased obviously with the increase of nitrate concentration, but the percentage of organic chloramines increased and was linearly correlated to nitrate concentration.

Formation of carbonaceous and nitrogenous disinfection by-products during monochloramination of oxytetracycline including N-Nitrosodimethylamine

AbstractFormation of typical volatile carbonaceous and nitrogenous disinfection by-products (C-DBPs and N-DBPs) during aqueous monochloramination of oxytetracycline (OTC) was investigated in this study. Impact factors including reaction time, pH, monochloramine (NH2Cl) dosages, and bromide concentrations were examined. The results showed that six DBPs including chloroform, dichloroacetonitrile, trichloronitromethane, 1,1-dichloropropanone, 1,1,1-trichloropropanone, especially extreme toxic N-Nitrosodimethylamine were found. Formation of these DBPs increased over time and monochloramine dosages with maximum yields given as 14.2, 4.3, 0.8, 2.1, 0.7, and 4.1 μg/mg at pH 7, respectively (μg/mg represents DBPs yields per mg of OTC). Solution pH exerted significant influence on the formation of all the DBPs species. Peak yields were found under circumneutral conditions. Production of bromine-substituted DBPs increased in the presence of bromide. Removal of presented OTC in waters should be implemented before ch...