Formation Characteristics of N-Nitrosodimethylamine during Chloramines of PolyDADMAC

Interactions of chloramine with organic nitrogen compounds during purification of water for drinking may generate carcinogenic N-nitrosodime-thylamine (NDMA) as byproduct, and it has been found that cationic amine-based water treatment polymers may be one of the important precursors of NDMA. We have analyzed experimentally the influence rule of NDMA formation during chlorination and disinfection, in order to provide technical support for reducing or even avoiding the formation of NDMA. The formation characteristics of nitrosamines during the chlorination of poly-diallyldimethylammonium chloride (polyDADMAC) have been studied during our experiments. The results show that the type of chlorinating agent is crucial for the generation of NDMA;if pH = 7, NDMA has the great potential formation;the NDMA potential formation increases with temperature. The yield of NDMA will be higher as the concentration of monochloramine is 1.5 to 2.5 times of the precursor;the variation of polymer with reaction time can explain the concentration of NDMA in terminal water of pipe network is higher than that in drinking water.

Determination of N-nitrosodimethylamine in drinking water by UPLC-MS/MS

The method for detecting N-nitrosodimethylamine （NDMA） in drinking water using ultra performance liquid chromatography （UPLC） coupled with tandem mass spectrometry （MS/MS） was improved by optimizing the clean-up procedure to remove the matrix interference in pretreatment process, and was then applied to a survey of NDMA in both raw and finished water samples from five water treatment plants in South China. The NDMA concentrations ranged from 4.7 to 15.1 ng/L in raw water samples, and from 4.68 to 46.9 ng/L in finished water. The NDMA concentration in raw water was found to be related with nitrite concentration, and during the treatment, the NDMA concentration increased following ozonation but decreased after subsequent activated carbon treatment.

Occurrence and removal of N-nitrosodimethylamine and its precursors in wastewater treatment plants in and around Shanghai

Six wastewater treatment plants （WWTPs） were investigated to evaluate the occurrence and removal of N-nitrosodimethylamine （NDMA）, NDMA formation potential （FP） and four specific NDMA precursors, dimethylamine （DMA）, trimethylamine （TMA）, dimethyl- formamide （DMFA） and dimethylaminobenzene （DMAB）. DMA and tertiary amines with DMA functional group commonly existed in municipal wastewater. Chemically enhanced primary process （CEPP） had no effect on removal of either NDMA or NDMA FP. In WWTPs with secondary treatment processes, considerable variability was observed in the removal of NDMA （19%-85%） and NDMA FP （16%-76%）, moreover, there was no definite relationship between the removal of NDMA and NDMA FP. DMA was well removed in all the six surveyed WWTPs; its removal efficiency was greater than 97%. For the removal of tertiary amines, biologic treatment processes with nitrification and denitrification had better removal efficiency than conventional activated sludge process. The best removal efficiencies for TMA, DMFA and DMAB were 95%, 68% and 72%, respectively. CEPP could remove 73% of TMA, 23% of DMFA and 36% of DMAB. After UV disinfection, only 17% of NDMA was removed due to low dosage of UV was applied in WWTP. Although chlorination could reduce NDMA precursors, NDMA concentration was actually increased after chlorination.

Factors controlling N-nitrosodimethylamine （NDMA） formation from dissolved organic matter

The formation of cancinogenic nitrosamines, esp. N-nitrosodimethylamine （NDMA） in water and wastewater treatment plants has drawn much attention in recent years. Dissolved organic matter from the transported Luan River water as water source of Tianjin was fractionated with different XAD resins and a series of ultra-filtration membranes with molecular weight （MW） cut-offs of 5k Da, 3k Da, and lk Da, respectively. The NDMA yields from the raw water and each fraction were measured to investigate their role in NDMA yield. Results indicated that the hydrophilic fraction had a higher NDMA yield than those of hydrophobic fraction and transphilic fraction. The fraction with MW below lk Da had a higher NDMA yield than that with larger MW. NDMA formation increased as the dissolved organic carbon （DOC） to dissolved organic nitrogen （DON） ratio decreased, which indicated that DON might serve as the real important precursor for NDMA. The correlation between NDMA yield and specific ultraviolet absorbance at 254nm （SUVA254） suggested that the latter might not represent the specific precursors for NDMA in the water. Besides the water quality, the influences of pH, disinfectant dosage, and disinfection contact time on the formation of NDMA were also examined. These results will help water treatment plants establish measures to control this harmful disinfection by-product.

Characterization of N-nitrosodimethylamine formation from the ozonation of ranitidine

N-nitrosodimethylamine（NDMA） is an emerging disinfection by-product which is formed during water disinfection in the presence of amine-based precursors. Ranitidine, as one kind of amine-based pharmaceuticals, has been identified as NDMA precursor with high NDMA molar conversion during chloramination. This study focused on the characterization of NDMA formation during ozonation of ranitidine. Influences of operational variables（ozone dose, pH value） and water matrix on NDMA generation as well as ranitidine degradation were evaluated. The results indicate high reactivity of ranitidine with ozone.Dimethylamine（DMA） and NDMA were generated due to ranitidine oxidation. High pH value caused more NDMA accumulation. NDMA formation was inhibited under acid conditions（pH ≤ 5） mainly due to the protonation of amines. Water matrix such as HCO-3and humic acid impacted NDMA generation due to UOH scavenging. Compared with UOH,ozone molecules dominated the productions of DMA and NDMA. However, UOH was a critical factor in NDMA degradation. Transformation products of ranitidine during ozonation were identified using gas chromatography–mass spectrometry. Among these products, just DMA and N,N-dimethylformamide could contribute to NDMA formation due to the DMA group in the molecular structures. The NDMA formation pathway from ranitidine ozonation was also proposed.

Apoptosis Induced by N-Nitrosamines in Two Cancer Cell Lines

In the present study, we investigated the induction of apoptosis by N-nitrosopyrrolidine (NPYR) and N-nitrosodimethy-lamine (NDMA) in two human cell lines: HL-60 (leukemia) and HepG2 (hepatoma). Apoptotic cells were identified by: 1) chromatin condensation, 2) flow cytometry analysis and 3) poly (ADP-ribose) polymerase cleavage. Both cell lines exhibited morphological changes consistent with apoptotic events following treatment with N-nitrosamines. Flow cytometry analysis showed that both N-nitrosamines induced apoptotic cell death in a concentration and time dependent- manner. NPYR was stronger than NDMA, since it induced a significant apoptotic cell death after 72 h starting from a concentration of 10 mM, whereas NDMA was effective at 27 mM. Furthermore, NPYR and NDMA caused the cleavage of PARP in HL-60 cells whereas no PARP cleavage was detected in HepG2 cells. However, NPYR- and NDMA-induced cell death in HepG2 cells was prevented by specific caspase inhibitors. Caspase-8 mediated main pathway and was responsible for 76% (NPYR) and 64% (NDMA) inhibition of apoptosis. The data demonstrate that NPYR and NDMA induce apoptosis in HL-60 and HepG2 cell lines via caspase-dependent pathway.

Intake of tobacco nitrosamines of smokers in various provinces of China and their cancer risk:A meta-analysis

Nitrosamines are a class of carcinogens which have been detected widely in food,water,some pharmaceuticals as well as tobacco.The objectives of this paper include reviewing the basic information on tobacco consumption and nitrosamine contents,and assessing the health risks of tobacco nitrosamines exposure to Chinese smokers.We searched the publications in English from“Web of Science”and those in Chinese from the“China National Knowledge Infrastructure”in 2022 and collected 151 literatures with valid information.The content of main nitrosamines in tobacco,including 4-(methylnitrosoamino)-1-(3-pyridyl)-1-butanone(NNK),N-nitrosonornicotine(NNN),N-nitrosoanatabine(NAT),N-nitrosoanabasine(NAB),total tobacco-specific nitrosamines(TSNA),and N-nitrosodimethylamine(NDMA)were summarized.The information of daily tobacco consumption of smokers in 30 provinces of China was also collected.Then,the intakes of NNN,NNK,NAT,NAB,TSNAs,and NDMA via tobacco smoke were estimated as 1534ng/day,591 ng/day,685 ng/day,81 ng/day,2543 ng/day,and 484 ng/day by adult smokers in30 provinces,respectively.The cancer risk(CR)values for NNN and NNK inhalation intake were further calculated as 1.44×10^(-5)and 1.95×10^(-4).The CR value for NDMA intake via tobacco smoke(inhalation:1.66×10^(-4))indicates that NDMA is similarly dangerous in tobacco smoke when compared with the TSNAs.In China,the CR values caused by average nitrosamines intake via various exposures and their order can be estimated as the following:smoke(3.75×10^(-4))>food(1.74×10^(-4))>drinking water(1.38×10^(-5)).Smokers in China averagely suffer 200%of extra cancer risk caused by nitrosamines in tobacco when compared with non-smokers.

Simultaneous removal of ammonia and N-nitrosamine precursors from high ammonia water by zeolite and powdered activated carbon

When adding sufficient chlorine to achieve breakpoint chlorination to source water containing high concentration of ammonia during drinking water treatment, high concentrations of disinfection by-products（DBPs） may form. If N-nitrosamine precursors are present, highly toxic N-nitrosamines, primarily N-nitrosodimethylamine（NDMA）, may also form. Removing their precursors before disinfection should be a more effective way to minimize these DBPs formation. In this study, zeolites and activated carbon were examined for ammonia and N-nitrosamine precursor removal when incorporated into drinking water treatment processes.The test results indicate that Mordenite zeolite can remove ammonia and five of seven N-nitrosamine precursors efficiently by single step adsorption test. The practical applicability was evaluated by simulation of typical drinking water treatment processes using six-gang stirring system. The Mordenite zeolite was applied at the steps of lime softening, alum coagulation, and alum coagulation with powdered activated carbon（PAC） sorption. While the lime softening process resulted in poor zeolite performance, alum coagulation did not impact ammonia and N-nitrosamine precursor removal. During alum coagulation, more than67% ammonia and 70%–100% N-nitrosamine precursors were removed by Mordenite zeolite（except 3-（dimethylaminomethyl）indole（DMAI） and 4-dimethylaminoantipyrine（DMAP））. PAC effectively removed DMAI and DMAP when added during alum coagulation. A combination of the zeolite and PAC selected efficiently removed ammonia and all tested seven N-nitrosamine precursors（dimethylamine（DMA）, ethylmethylamine（EMA）, diethylamine（DEA）, dipropylamine（DPA）, trimethylamine（TMA）, DMAP, and DMAI） during the alum coagulation process.

Factors influencing the photodegradation of Nnitrosodimethylamine in drinking water

In order to provide basic data for practical application,photodegradation experiment of Nnitrosodimethylamine(NDMA)in aqueous solution was carried out with a low-pressure Hg lamp.Effects of the initial concentration of NDMA,solution pH,dissolved oxygen,and the presence of humic acid on NDMA photodegradation were investigated.NDMA at various initial concentrations selected in this study was almost completely photodegraded by UV irradiation within 20 min,except that at 1.07 mmol/L,NDMA could be photodegraded almost completely in the acidic and neutral solutions,while the removal efficiency decreased remarkably in the alkaline solution.Dissolved oxygen enhanced the NDMA photodegradation,and the presence of humic acid inhibited the degradation of NDMA.Depending on the initial concentration of NDMA,NDMA photodegradation by UV obeyed the pseudo-first-order kinetics.Dimethylamine,nitrite,and nitrate were detected as the photodegradation products of NDMA.^(1)O_(2) was found to be the reactive oxygen species present in the NDMA photodegradation process by UV,based on the inhibiting experiments using tert-butanol and sodium azide.

A photolysis coefficient for characterizing the response of aqueous constituents to photolysis

UV photolysis and UV based advanced oxidation processes （AOPs） are gaining more and more attention for drinking water treatment. Quantum yield （Ф） and molar absorption coefficient （ε） are the two critical parameters measuring the effectiveness of photolysis of a compound. The product of the two was proposed as a fundamental measure of a constituent＇s amenability to transformation by photolysis. It was shown that this product, named the photolysis coefficient, kp, can be determined using standard bench tests and captures the properties that govern a constituent＇s transformation when exposed to light. The development showed the photolysis coefficient to be equally useful for microbiological, inorganic and organic constituents. Values of kp calculated by the authors based on quantum yield and molar absorption coefficient data from the literature were summarized. Photolysis coefficients among microorganisms ranged from 8500 to more than 600000 and are far higher than for inorganic and organic compounds, which varied over a range of approximately 10 to 1000 and are much less sensitive to UV photolysis than the microorganisms.