Formation of halonitromethanes from methylamine in the presence of bromide during UV/Cl2 disinfection.

The UV/Cl2 process is commonly used to achieve a multiple-barrier disinfection and maintain residuals. The study chose methylamine as a precursor to study the formation of high-toxic halonitromethanes (HNMs) in the presence of bromide ions (Br-) during UV/Cl2 disinfection. The maximum yield of HNMs increased first and then decreased with increasing concentration of Br-. An excessively high concentration of Br- induced the maximum yield of HNMs in advance. The maximum bromine incorporation factor (BIF) increased, while the maximum bromine utilization factor (BUF) decreased with the increase of Br- concentration. The maximum yield of HNMs decreased as pH value increased from 6.0 to 8.0 due to the deprotonation process. The BUF value remained relatively higher under an acidic condition, while pH value had no evident influence on the BIF value. The maximum yield of HNMs and value of BUF maximized at a Cl2:Br- ratio of 12.5, whereas the BIF value remained relatively higher at low Cl2:Br- ratios (2.5 and 5). The amino group in methylamine was first halogenated, and then released into solution as inorganic nitrogen by the rupture of C-N bond or transformed to nitro group by oxidation and elimination pathways. The maximum yield of HNMs in real waters was higher than that in pure water due to the high content of dissolved organic carbon. Two real waters were sampled to verify the law of HNMs formation. This study helps to understand the HNMs formation (especially brominated species) when the UV/Cl2 process is adopted as a disinfection technique.

Formation and transformation of halonitromethanes from dimethylamine in the presence of bromide during the UV/chlorine disinfection.

Halonitromethanes (HNMs) is a typical class of nitrogenous disinfection byproducts with high toxicity. The effect of Br- on the formation and transformation of HNMs from dimethylamine (DMA) during the ultraviolet (UV)/chlorine disinfection has been investigated in current study. Results reveal that only chloronitromethane, dichloronitromethane and trichloronitromethane (TCNM) could be found during the UV/chlorine disinfection. Whereas in the presence of Br-, nine species of HNMs could be observed simultaneously. When Br- concentration increased from 0 to 15.0 mg L-1, the predominant species of HNMs were gradually changed from TCNM to dibromonitromethane and tribromonitromethane, which contributed to 23.37% and 31.07% of total HNMs concentration at 15 mg L-1 Br-, respectively. The presence of Br- not only shifted the chlorinated-HNMs (Cl-HNMs) towards brominated-HNMs (Br-HNMs) but also affected the dominant species and total concentration of HNMs. When Br- concentration was 4.0 mg L-1, the formation of HNMs decreased with the increase of pH from 6.0 to 8.0 and increased with the increase of free chlorine and DMA. When free chlorine concentration rose from 0.25 to 1.1 mmol L-1, Br-HNMs were shifted to Br(Cl)-HNMs and then to Cl-HNMs. According to the findings, possible formation and transformation pathways of HNMs from DMA were proposed in the presence of Br- during the UV/chlorine disinfection. Finally, it was proved that the effect of Br- on the trend of HNMs in real water was similar to that in deionized water, but higher HNMs concentrations and delayed peak time were observed in real water. This study can provide the scientific evidence and fundamental data for the applications of UV/chlorine disinfection in the treatment of water containing Br-.

Impact of tryptophan on the formation of TCNM in the process of UV/chlorine disinfection.

Low-pressure (LP) UV treatment after chlorine disinfection was associated with enhanced formation of trichloronitromethane (TCNM), a halonitromethane disinfection by-product (DBP), due to the chlorination of tryptophan. Evidence was found that the concentration of TCNM from tryptophan increased quickly to the maximum for the first instance. Moreover, the increase of TCNM under UV exceeded 10 times than under dark. Then, it was found to have an obvious decrease in the formation of TCNM, even finally hardly disappear. In order to elucidate reasons for this phenomenon, the effects of light intensity, initial tryptophan concentration, free chlorine concentration, pH, and tert-butanol (TBA) on the formation of TCNM were investigated under UV/chlorine treatment. Finally, the effects of tryptophan on the formation of TCNM and the direct photodegradation of TCNM under LP UV irradiation were studied for analyzing the possible pathways of TCNM formation from amino acid. Since amino acids are very common in water sources, further research into chemical oxidation of these species by LP UV and chlorine is recommended. It can help us to find the precursors of TCNM formation and reduce the risk of TCNM formation for drinking water and wastewater utilities.