Enhancing trace acrylamide analysis by bromine derivatization coupled with direct-immersion solid-phase microextraction in drinking water.

Acrylamide is a neurotoxic and genotoxic compound. It is abundant in drinking water because of the usage of polyacrylamide. Its high polarity and small molecular weight characteristics make it difficult to be extracted and analysed. In this study, a novel method was optimized for the determination of trace acrylamide in drinking water. The optimized method, uses bromine derivatization, can avoid false analysis of co-extractives and precursors effectively by transferring acrylamide to 2-bromopropenamide. The 2-bromopropenamide was extracted from water samples using DI-SPME and further analysed by GC-MS. This optimized method uses CAR/PDMS coating SPME fibre to extract at 55°C for 45 min after the addition of 12 g Na2SO4, and then desorbs the extractions in GC injector at 260°C for 3 min. The detection limit was 0.05 µg/L with linearity ranging from 0.5 to 500 µg/L. The repeatability and reproducibility relative standard deviation were 7.30% and 8.50%, respectively. The spiking recovery of tap water samples ranged from 100% to 106%. These results confirmed that this novel method was more precise and accurate than the previously reported SPME methods that used to analyse trace acrylamide in drinking water. The concentrations of acrylamide in the collected samples from clarification and filtration units were 0.80 and 0.71 g/L respectively.

Degradation of acrylamide during chlorination as a precursor of haloacetonitriles and haloacetamides.

Acrylamide is a monomer of polyacrylamide, which is widely used in the water treatment process as a flocculant. The degradation kinetics and formation of disinfection by-products (DBPs) during acrylamide chlorination were investigated in this study. The reaction between chlorine and acrylamide followed a pseudo-first-order kinetics. A kinetic model regarding acrylamide chlorination was established and the rate constants of each predominant elementary reaction (i.e., the base-catalyzed reaction of acrylamide with ClO- as well as the reactions of acrylamide with HOCl and ClO-) were calculated as 7.89×107M-2h-1, 7.72×101M-1h-1, and 1.65×103M-1h-1, respectively. The presence of Br- in water led to the formation of HOBr and accelerated the rate of acrylamide degradation by chlorine. The reaction rate constant of acrylamide with HOBr was calculated as 1.33×103M-1h-1. The degradation pathways of acrylamide chlorination were proposed according to the intermediates identified using ultra-performance liquid chromatography and electrospray ionization-quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF/MS). Five chlorinated DBPs including chloroform (CF), dichloroacetonitrile (DCAN), trichloroacetonitrile (TCAN), dichloroacetamide (DCAcAm), and trichloroacetamide (TCAcAm) were identified during acrylamide chlorination. The formation of CF, DCAN, DCAcAm, and TCAcAm kept increasing, while that of TCAN increased and then decreased with increasing reaction time. As the chlorine dosage increased from 0.75 to 4.5mM, DCAN became the dominant DBP. Large amounts of CF, DCAN, and TCAN were formed at basic pHs. The hydrolysis of DCAN and TCAN led to the formation of DCAcAm and TCAcAm, respectively. The results of this study elucidated that acrylamide can be a precursor for the formation of haloacetonitriles (HANs) and haloacetamides (HAcAms) during drinking water treatment.

[Formation of Disinfection By-Products During Chlor(am)ination of Danjiangkou Reservoir Water and Comparison of Disinfection Processes].

This study discussed the formation of volatile carbonaceous disinfection by-products (DBPs) and nitrogenous DBPs during chlor(am) ination of Danjingkou Reservoir water which was the source of the Middle Route Project of South-to-North Water Diversion Project. The effects of disinfection methods, disinfectant dosage, reaction time, pH values and bromide ion concentration were investigated. And the disinfection parameters were optimized. Four DBPs, including chloroform (CF), bromodichloromethane (BDCM), dichloroacetonitrile(DCAN) and trichloronitromethane(TCNM), were observed during the chlorination. But only CF and TCNM were detected during the chloramination of water. The disinfection by-product (DBP) concentration from chlorination is 7. 5 times higher than that from chloramination, and the yield of DBPs from short time chlorination then chloramination is in between the first two methods. All kinds of DBPs detected increased with the dosage of increasing chlorine, but the increases slowed down when the dosage was higher than 2 mg . L -1. The formation of CF varied a little as the dosage of chloramine increasing. TCNM was detected when the chloramine dosage was greater than 2 mg . L -1. As reaction time going on, chlorine decayed much faster than chloramine, while DBP formation under chlorination was faster than that of chloramination. THM produced by chlorine increased with the increasing pH, while chloramination showed no obvious changes. As the bromide ion increasing, the species of DBPs transformed from chlorinated DBPs to brominated ones, and the total yield of DBPs increased during both chlorination and chloramination, but the former one was obviously more than that of the latter one. In order to reduce the risk of DBP formation, the chloramination is suggested in the treatment of water from Danjiangkou Reservoir. And if chlorination is applied, the disinfectant dosage should be controlled seriously.