Electrochemical dechlorination of chlorobenzenes in the presence of various arene mediators such as naphthalene, biphenyl, phenanthrene, anthracene, and pyrene, was studied. The amount of mediator required was able to be reduced to 0.01 equiv. for all mediators except for anthracene, with the complete dechlorination of mono-, 1,3-di- and 1,2,4-trichlorobenzene still achieved. This catalytic amount of mediator plays an important role in accelerating the dechlorination through the rapid formation of radical anions prior to reduction of the chlorobenzenes.
Mefenamic acid (Mfe) is one of the most frequently detected nonsteroidal anti-inflammatory drugs in the environment. This study investigated the kinetics and the transformation by-products of Mfe during aqueous chlorination. The potential ecotoxicity of the transformation by-products was also evaluated. In the kinetic study, the second-order rate constant (kapp) for the reaction between Mfe and free available chlorine (FAC) was determined at 25 ± 0.1 °C. The result indicated that the degradation of Mfe by FAC is highly pH-dependent. When the pH was increased from 6 to 8, it was found that the kapp for the reaction between Mfe and FAC was decreased from 16.44 to 4.4 M(-1) s(-1). Characterization of the transformation by-products formed during the chlorination of Mfe was carried out using liquid chromatography-quadrupole time-of-flight accurate mass spectrometry. Four major transformation by-products were identified. These transformation by-products were mainly formed through hydroxylation, chlorination and oxidation reactions. Ecotoxicity assessment revealed that transformation by-products, particularly monohydroxylated Mfe which is more toxic than Mfe, can be formed during aqueous chlorination.
A modeling procedure that predicts trihalomethane (THM) formation from field sampling at the treatment plant and along its distribution system using Tampin district, Negeri Sembilan and Sabak Bernam district, Selangor as sources of data were studied and developed. Using Pearson method of correlation, the organic matter measured as TOC showed a positive correlation with formation of THM (r=0.380,P=0.0001 for Tampin and r=0.478,P=0.0001 for Sabak Bernam). Similar positive correlation was also obtained for pH in both districts with Tampin (r=0.362,P=0.0010) and Sabak Bernam (r=0.215,P=0.0010). Chlorine dosage was also found to have low correlation with formation of THM for the two districts with Tampin (r=0.233,P=0.0230) and Sabak Bernam (r=0.505,P=0.0001). Distance from treatment plant was found to have correlation with formation of THM for Tampin district with r=0.353 and P=0.0010. Other parameters such as turbidity, ammonia, temperature and residue chlorine were found to have no correlation with formation of THM. Linear and non-linear models were developed for these two districts. The results obtained were validated using three different sets of field data obtained from own source and district of Seremban (Pantai and Sg. Terip), Negeri Sembilan. Validation results indicated that there was significant difference in the predictive and determined values of THM when two sets of data from districts of Seremban were used with an exception of field data of Sg. Terip for non-linear model developed for district of Tampin. It was found that a non-linear model is slightly better than linear model in terms of percentage prediction errors. The models developed were site specific and the predictive capabilities in the distribution systems vary with different environmental conditions.
This study investigated the reaction kinetics and mechanism of the degradation of 5,5-diphenylhydantoin (DPH) during conventional chlorination and UV/chlorination. DPH is one of the antiepileptic drugs, which has frequently been detected in the aquatic environment. For chlorination, the second-order rate constant for the reaction between DPH and free active chlorine (FAC) was determined at pH 5 to 8. At pH 6 to 8, the efficiency of chlorination in the removal of DPH was found to be dominated by the reaction involving hypochlorous acid (HOCl). The result also showed that anionic species of DPH was more reactive toward FAC as compared with neutral DPH. For UV/chlorination, the effect of FAC dosage and pH on the degradation of DPH was evaluated. UV/chlorination is a more effective method for removing DPH as compared with conventional chlorination and UV irradiation. The DPH degradation rate was found to increase with increasing FAC concentration. On the other hand, the degradation of DPH was found to be more favorable under the acidic condition. Based on the identified transformation by-products, DPH was found to be degraded through the reaction at imidazolidine-2,4-dione moiety of DPH for both chlorination and UV/chlorination. Toxicity study on the chlorination and UV/chlorination-treated DPH solutions suggested that UV/chlorination is a more efficient method for reducing the toxicity of DPH.
This study investigated the reaction kinetics and the transformation by-products of acebutolol during aqueous chlorination. Acebutolol is one of the commonly used β-blockers for the treatment of cardiovascular diseases. It has been frequently detected in the aquatic environment. In the kinetics study, the second-order rate constant for the reaction between acebutolol and chlorine (k app) was determined at 25 ± 0.1 °C. The degradation of acebutolol by free available chlorine was highly pH dependence. When the pH increased from 6 to 8, it was found that the k app for the reaction between acebutolol and free available chlorine was increased from 1.68 to 11.2 M(-1) min(-1). By comparing with the reported k app values, the reactivity of acebutolol toward free available chlorine was found to be higher than atenolol and metoprolol but lower than nadolol and propranolol. Characterization of the transformation by-products formed during the chlorination of acebutolol was carried out using liquid chromatography-quadrupole time-of-flight high-resolution mass spectrometry. Seven major transformation by-products were identified. These transformation by-products were mainly formed through dealkylation, hydroxylation, chlorination, and oxidation reactions.