Exploring Br-'s roles on non-brominated NDMA formation during ozonation: Reactive oxygen species contribution and brominated intermediate path validation.

Bromide ions (Br-) affected non-brominated nitroso-dimethylamine (NDMA) formation during ozonation, but the mechanism is still unclear. 1,1,1',1'-tetramethyl-4,4'-(methylene-di-p-phenylene) di-semicarbazide (TMDS) was chosen to further probe this problem. The results indicated that low levels of Br- (≤20 µM) enhanced NDMA from 3.27 to 7.56 µg/L, while its amount slightly dropped to 6.22 µg/L raising Br- to 100 µM. It was experimentally verified that intermediates 1,1-dimethylsemicarbazide (DMSC) and 1,1-dimethylhydrazine (UDMH) played important roles on promoting NDMA generation, whose contribution rates were 40.2% and 32.2%, respectively. The brominated substances with higher NDMA molar yields were detected. ∙OH reduced NDMA formation without Br-, while it played promotion role with Br-; the corresponding contribution rates were - 26.9% and 29.2%, respectively. No matter with or without Br-, both ∙O2- and lO2 brought a boost to NDMA formation, their contribution ratios were 34.9% and 58.1% without Br-, while raised significantly to 64.6% and 81.5% when Br- existed. Br- not only facilitated NDMA formation, but also benefited the degradation of TMDS. Based on the calculation results and intermediates detected, the influence mechanisms of Br- were proposed. The results would provide theoretical basis and technical guarantee for treating NDMA precursors and bromide co-existing water in the future.

Synthesis of Yttrium Oxide Nanoneedles with Carbon Dioxide Carbonization.

In this study, a CO2 carbonization method is introduced for the preparation of 1D yttrium oxide powders. Using YCl3 as the raw material, sodium hydroxide was initially used to completely precipitate Y3+ into yttrium hydroxide, and then CO2 was introduced into the yttrium hydroxide slurry for homogenization-like carbonization to obtain yttrium carbonate precipitation. Then, by studying the effects of carbonization conditions, such as the temperature, CO2 flow rate, and stirring speed, on the morphology and phases of yttrium carbonate, the temperature was observed to exert a greater effect than the other experimental parameters on the morphology and structure of the carbonized products. Finally, Y2(CO3)3·2H2O nanoneedles were obtained at optimal conditions. The carbonized crystals of the acicular yttrium carbonate precipitate because of the solution supersaturation and then quickly complete their crystal growth process through the oriented attachment (OA) and Ostwald ripening (OR) mechanisms. After heat treatment, yttrium carbonate retained a good crystal morphology and produced Y2O3 nanoneedles with a length of 1-2 µm and a width of 20-30 nm.

NDMA formation during ozonation of DMAPA: Influencing factors, mechanisms, and new pathway exploration.

Aliphatic amines, common constituents that contribute to dissolved organic nitrogen (DON), can quickly react with ozone due to the lone electron pair on the nitrogen atom and this may produce carcinogen N-Nitrosodimethylamine (NDMA). 3-(Dimethylamino)-1-propylamine (DMAPA) was chosen as a representative to elucidate the NDMA formation characteristics, kinetic rates, reaction pathways, and influencing factors during ozonation in this study. The results demonstrated that NDMA generated directly from DMAPA during ozonation. Moreover, the NDMA yields increased with ozone dosages. The NDMA molar yield increased and then decreased when the pH raised from 5 to 9, achieving the maximum value at pH 8. Hydroxyl radical (∙OH) played a promotional role in NDMA formation, and its scavenger dramatically cut down its yields. Low levels of Br- facilitated NDMA formation, while the value significantly reduced when Br- was up to 1 mM. The NDMA amount was slightly raised by NO2-, but it was inhibited by NH4+ and NO3-. Moreover, it was also depressed by co-existing components in actual lake water. Based on the result of the Gaussian calculation, the LC-MS/MS and GC-MS analysis, four possible transformation pathways were proposed. The radical recombination was verified to be the primary pathway for ozone promoting NDMA formation from DMAPA.

NDMA formation during ozonation of metformin: Roles of ozone and hydroxyl radicals.

Metformin, a high-consumed pharmaceutical for diabetes, has been reported to generate carcinogenic nitroso-dimethylamine (NDMA) during treatment of its containing wastewater. However, whether it would produce NDMA during ozonation or not is unclear, let alone discriminate roles of ozone (O3) and hydroxyl radicals (OH). In this paper, effects of ozonation on NDMA formation from metformin were investigated, roles of O3 and OH were also distinguished by adding tert-butyl alcohol (tBA) as OH scavenger. Moreover, various influencing factors and reaction mechanisms were demonstrated. The results indicated that NDMA could be directly formed from metformin during ozonation, the addition of OH scavenger significantly enhanced its formation (0-46.2 ng/L vs 0-139.1 ng/L). The formation of NDMA by O3 and OH was more affected by bromide and HCO3- than those with only O3; while the impacts of pH and sulphate on the latter were more notable. No matter without/with tBA in the solution, the formed NDMA during ozonation of metformin increased with raising pH (from 5 to 9) and achieved the maximum 69.6 ng/L and 235.9 ng/L at pH 9, respectively; small amount of bromide (0.1 µM) promoted NDMA production, high levels of bromide (10 µM) inhibited its formation; the existence of HCO3- enhanced the amounts of NDMA from 44.5 to 73.5 ng/L (raised by 65.2%) by O3 and OH and from 102.9 to 130 ng/L with only O3 (raised by 26.3%); with the addition of sulphate, NDMA concentration raised by 43.8% by O3 and OH, while the value was high up to 134.6% with only O3. Based on the result of UPLC-Q-TOF and density functional theory, the oxidation intermediates were identified and possible transformation pathways of metformin during ozonation were proposed. The findings in this paper would provide reference when treating metformin-containing water in future.

Validation of the promotion mechanism between bromide and UDMH to form NDMA during ozonation.

Unsymmetrical dimethylhydrazine (UDMH) is found to generate substantial carcinogenic nitroso-dimethylamine (NDMA) during ozonation, moreover, its formation is promoted by ubiquitous bromide ions (Br-) in water matrixes, but the mechanism is still unclear. In this study, effects of Br- on NDMA formation during ozonation of UDMH were studied, meanwhile, its promotion pathways were also determined. The results demonstrated that Br- promoted NDMA formation from UDMH during ozonation, the formation rate constant with Br- is over 7 times of that without Br-. NDMA amount raised from 142.5 to 327.5 µg/L when Br- dosages increased from 0 to 100 µM. No matter with or without Br-, the augment of O3 dosages facilitated NDMA formation; the maximum value was achieved at pH 8. NDMA decreased dramatically from 173.8 to 123.5 µg/L with HCO3- raising from 0 to 160 µM, while increasing remarkably to 222.5 µg/L with SO42- dosing. In addition, NOM inhibited NDMA formation from UDMH during ozonation. The mass spectrum of LC-MS/MS verified that the generation of Br-UDMH was main cause for promoting NDMA formation. Moreover, hypobromous acid (HBrO) was confirmed to be responsible for Br-UDMH formation. In addition, the position that oxidants and Br- attacked was demonstrated based on Gaussian calculation. The results of this study could provide theoretical basis for the application of ozonation in bromine-containing water matrixes.