Modifying NaY Zeolite with Metal Oxide by Microwave Irradiation:Influence on the Adsorption and Decomposition of N-nitrosamines

Coating MgO.br ZrO2 on zeolite NaY accelerated decomposition of N-nitrosodimethylamine and N-nitrosopyrrolidine, resulting from variation of the surface state such as generation of basic sites.

Metabolism Study on Tobacco-specific N-Nitrosamines in Rabbit by Solid-phase Extraction and Liquid Chromatography-electrospray Ionization-mass Spectrometry Method

Metabolism of four tobacco-specific N-nitrosamines （TSNAs）, N＇-nitrosonornicotine （NNN）, N＇-nitrosoanatabine （NAT）, N＇-nitrosoanabasine （NAB） and 4-（methyl nitrosamino）-1- （3-pyridyl）-1-butanone （NNK） was studied by solid-phase extraction （SPE） and liquid chromato- graphy-electrospray ionization-mass spectrometry （LC-ESI-MS）. SPE and LC-ESI-MS method was evaluated to be rapid, simple, sensitive and selective for analysis of TSNAs in rabbit serum. The doses of TSNAs administrated were 4.666 μg/kg and 11.665 μg/kg according to different levels in cigarettes. Metabolic curves of four TSNAs and 4-（methyl nitrosamino）-1-（3-pyridyl）- 1-butanone （NNAL）, the metabolite of NNK, were obtained.

Rapid and Simple Extraction Method for Volatile N-Nitrosamines in Meat Products

A new methodology for extraction, pre-concentration and analysis of volatile nitrosamines in meat-derived products was developed and compared with conventional methods (Distillation and two-step solid-phase extraction). The samples (canned sausages, cured meat, luncheon and smoked meat) were treated with an aqueous sodium hydroxide (NaOH) by autoclaving at 121°C for 10 min and extracted by liquid-liquid extraction with dichloromethane, then the nitrosamines were pre-concentrated using activated silica. Then, gas chromatography coupled with flame ionization detector was used for the separation and determination of the different nitrosamines contained in a real sample and gas chromatography with mass spectrometry detection was used as the confirmation technique. The newly invented autoclaving method allowed the determination of nitrosamine compounds at trace levels with limit of detection ranged from 0.077 to 0.18 ppb and quantitation limits were from 0.26 to 0.6 ppb for all nitrosamines, and found to be superior to the conventional ones, yielding approximately about 10%-20% increasing in the recovery compared with the mean recovery obtained when applying conventional methods.

Determination of Seven Volatile N-Nitrosamines in Fast Food

In this study, various fast food samples, including raw meat, cured meat, grilled meat, fried meat, smoked meat and canned meat products, were analyzed for the determination of the seven volatile N-nitrosamines. The samples were treated with an aqueous sodium hydroxide (NaOH) by autoclaving at 121°C for 10 min and extracted by liquid-liquid extraction with dichloromethane, and then the nitrosamines were pre-concentrated by using activated silica. Then, gas chromatography coupled with flame ionization detector was used for the separation and determination of the different nitrosamines contained in a real sample. The applied method allowed the determination of nitrosamine compounds at trace levels with limit of detection ranging from 0.077 to 0.18 ppb, and quantitation limits were from 0.26 to 0.60 ppb for all nitrosamines. The total concentrations of the seven nitrosamines in the studied meat samples ranged from 2.60 to 13.28 μg/kg.

A Rapid, Validated RP-HPLC Method for the Determination of Seven Volatile N-Nitrosamines in Meat

The present work reports a rapid reversed-phase high-performance liquid chromatography (RP-HPLC) method for the determination of seven volatile N-nitrosamines namely N-nitrosodimethylamine (NDMA), N-nitrosomethylethylamine (NMEA), N-nitrosodiethylamine (NDEA), N-nitrosodiproylamine (NDPA), N-nitrosodi butylamine (NDBA), N-nitrosopiperidine (NPIP) and N-nitrosopyrrolidine (NPYR) for monitoring food safety. A strategic experimental approach was implemented for the method development. The desired chromatographic separation was achieved on a Symmetry C18 (4.6 × 150 mm, 5 μm) column using gradient elution. The optimized mobile phase consisted of the 10 mM ammonium hydroxide pH = 8.9 and acetonitrile. The eluted compounds were monitored at 231 nm wavelength using spectrophotometric detector. The developed method separated seven compounds from each other within a run time of 10 min. The method is effective for the determination of presence of these carcinogenic compounds. The average extraction recovery of seven nitrosamines was found 84.5%;the precision of method was found less than 2.7% and accuracy was found between 95%-102.5%. The assay could be applied in food monitoring safety.

Detecting N-nitrosamines in water treatment plants and distribution systems in China using ultra-performance liquid chromatography-tandem mass spectrometry

N-nitrosodimethylamine （NDMA） and several other N-nitrosamines have been detected as disinfection by-products in drinking waters in many countries around the world. An ultra-performance liquid chromatography- tandem mass spectrometry method with solid phase extraction sample preparation was developed to study the occurrence of N-nitrosamines in several water treatment plants and distribution systems in China. Isotope labeled N-nitrosodi-n-propylamine-dl4 （NDPA-dl4） was selected as the internal standard for quantification. The solid phase extraction procedures including pH, enrichment process and MS/MS parameters including capillary voltage, cone gas flow, cone voltage, collision energy were optimized to give average recoveries of 26% to 112% for nine N- nitrosamine species. The instrument detection limits were estimated to range from 0.5 to 5μg.L-1 for the nine N- nitrosamine species. NDMA and several other N-nitrosa- mines were found at fairly high concentrations in several water treatment plants and distribution systems. NDMA was found in all locations, and the highest concentrations in cities B, G, T, and W were 3.0, 35.7, 21.3, and 19.7 ng. L 1, respectively. A wide range of N-nitrosamines concentrations and species were observed in different locations. Higher concentrations of N-nitrosamines were detected in distribution systems that were further away from the treatment plants, suggesting that the contact time between the residual disinfectant and natural organic matter may play an important role in the formation of these compounds.

Strong selective adsorption of N-nitrosamines on zeolites

With the functional group of -N-N=O, N-ni-trosamines are well known to constitute a serious health risk[1]. These toxicant chemicals not only give rise to poisoning sometimes[2], but also play an important role in causing cancer in almost all organs of experimental animals and are therefore likely to be related to human beings, since they have the similar metabolism and meta-balin to those animals[3]. Gaseous nitrogen oxides like NO2, N2O3 and N2O4 are reportedly to react with-secondary amines and form N-nitrosamines in environment[4], and some foods, such as beer and salted fish, contain a high concentration of N-nitrosamines and their precursors. However, tobacco and cigarette smoke are believed to be the largest N-nitrosamines pollution for human beings besides the industrial working place. N-nitrosamines are considered important contributors to the total burden of carcinogens resulting from tobacco, especially tobacco smoke, because they can be deposited directly into the blood following inhalation

肉制品中亚销胺的形成机理及其影响因素分析(英文)

Nitrite is one of the most important additives in meat products. In most countries the use of the additive is limited and either the ingoing or the residual amounts are regulated by laws. N-nitrosamines are formed by amines or amino acids with nitrite in meat. Investigations on the occurrence of N-nitrosamines in meat products have been carried out in many countries around the world. In this paper, mechanism of N-nitrosamine formation and its corresponding influence factors in meat products were reviewed. The contents of N-nitrosamines in meat and analytical techniques for the compounds were also described.

Analysis of <i>N</i>-Nitrosamine Migration from Rubber Teats and Soothers

A testing method for N-nitrosamines and N-nitrosatable substances in rubber teats and soothers was modified. N-Nitrosamines are generally analyzed using either a nitrogen chemiluminescence detector (NCD) or a thermal energy analyzer (TEA). However, because few testing laboratories are equipped with these devices, it is difficult to conduct these tests. Therefore, an analysis method for N-nitrosamines using the more widespread gas chromatography-mass spectrometry (GC-MS) method was improved. In addition, EN 12868 was used to prepare the test solutions because of its worldwide use and compliance with EU regulations. Using GC-MS, EN 12868 method targeting ten kinds of N-nitrosamines was modified. The determination limits of the method were 1.0 -1.5 μg/kg for N-nitrosamines and 4 -6 μg/kg for N-nitrosatable substances. Quantification was possible at 1/5 or less and 1/15 or less, respectively, of the regulation values listed in EU Directive 93/11/EEC. In terms of application, there were no problems with the selectivity of the detector. The recoveries were 58% -109% for N-nitrosamines and 59% -102% for N-nitrosatable substances. Screening and verification were possible by measuring the amount of secondary amines in the boiled solution and migration solution.

Electrochemical Reduction Determination of N-Nitrosodiphenylamine in Food Based on Graphene Electrode Material

As a group of the most notorious carcinogens,N-nitrosamines(NAs)are highly toxic and usually involved in healthy issue of human daily life.An electrochemical sensor for N-nitrosodiphenylamine(NDPhA)detection was constructed based on graphene electrode material.The graphene was facilely obtained by direct reduction of graphene oxide(GO)with hydrazine hydrate,and further coated on the surface of the glassy carbon electrode(GCE)to fabricate the electrochemical sensor for NDPhA analysis in food samples.The present sensor showed excellent sensitivity and selectivity for the electrochemical determination of NDPhA under a reduction manner with the detection limit of 0.6μmol/L.It was also successfully used in beer and ham food samples with satisfactory recovery results.

Monthly survey of N-nitrosamine yield in a conventional water treatment plant in North China

A sampling campaign was conducted monthly to investigate the occurrence of N-nitrosamines at a conventional water treatment plant in one city in North China.The yield of N-nitrosamines in the treated water indicated precursors changed greatly after the source water switching.Average concentrations of N-nitrosodimethylamine（NDMA）,N-nitrosomorpholine（NMOR）,and N-nitrosopyrrolidine（NPYR） in the finished water were6.9,3.3,and 3.1 ng/L,respectively,from June to October when the Luan River water was used as source water,while those of NDMA,N-nitrosomethylethylamine（NMEA）,and NPYR in the finished water were 10.1,4.9,and 4.7 ng/L,respectively,from November to next April when the Yellow River was used.NDMA concentration in the finished water was frequently over the 10 ng/L,i.e.,the notification level of California,USA,which indicated a considerable threat to public health.Weak correlations were observed between N-nitrosamine yield and typical water quality parameters except for the dissolved organic nitrogen.

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.

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.

Characterization of dissolved organic matter as N-nitrosamine precursors based on hydrophobicity, molecular weight and fluorescence

It is very important to identify the dominant precursors for N-nitrosamine formation from bulk organic matter, to enhance the understanding of N-nitrosamine formation pathways in water treatment plants and allow the development of practical treatment technologies. In this study, dissolved organic matter （DOM） from two source waters was fractionated with XAD resins and ultra- filtration membranes. The N-nitrosamine formation potential （FP） （ng of N-nitrosamines formed per mg of dissolved organic carbon （DOC）） from raw water and each fraction were measured and correlated with the fluorescence excitation-emission matrix （EEM）, molecular weight （MW） and other assays. The results showed that the hydrophilic fraction had N-nitrosamine FP 1.3 to 3.5 times higher than the hydrophobic fraction from both source waters. The DOM fraction with low MW was the dominant fraction in these two source waters and contributed more precursors for N-nitrosamine formation than the larger MW fraction. The EEM spectra indicated there were notable amounts of soluble microbial products （SMPs） and aromatic proteins in the two studied rivers, which probably originated from wastewater discharge. The SMPs tended to be more closely correlated with N-nitrosodimethylamine formation potential than the other DOM components. Higher N-nitrosamine FP were also related to fractions with lower DOC/DON ratios and lower SUVA254 values.

N-Nitrosamine formation from chloramination of two common ionic liquids

Ionic liquids(ILs)are a class of solvents increasingly used as"green chemicals."Widespread applications of ILs have led to concerns about their accidental entry to the environment.ILs have been assessed for some environmental impacts;however,little has been done to characterize their potential impacts on drinking water if ILs accidentally enter surface water.IL cations are often aromatic or alkyl quaternary amines that resemble structures of previously confirmed N-nitrosamine(NA)precursors.Therefore,this study has evaluated two common ILs,1-ethyl-3-methylimidazolium bromide(EMIm Br)and 1-ethyl-1-methylpyrrolidinium bromide(EMPyr Br),for their NA formation potential.Each IL species was reacted with pre-formed monochloramine under various laboratory conditions.The reaction mixtures were extracted using liquid–liquid extraction and analyzed for NAs using high performance liquid chromatography tandem mass spectrometry.At low concentration of IL(250μmol/L),the yields of NAs(NMEA or NPyr)increased with increasing doses of monochloramine from both IL species.The total NA yield was as high as 2.5±0.3 ng/mg from EMIm Br,and as high as 8.6±0.8 ng/mg from EMPyr Br.At high concentration of IL(5 mmol/L),the NA yield reached a maximum at 2.5 mmol/L NH2Cl,and then decreased with subsequent increases in the reactant concentrations,demonstrating ILs’solvent effects.This study re-emphasizes the importance of preventing discharge of ILs to water bodies to prevent secondary impacts on drinking water.

One representative water supply system in China with nitrosamine concern: Challenges and treatment strategies

Four sampling campaigns were conducted in two years to understand the fluctuation of N-Nitrosamines(NAs) and their precursors in one drinking water treatment plant(DWTP) in East China in different seasons.This water supply system has been facing several nitrosamine challenges related with source water, including the switch of water source,high concentration of ammonium, formed NAs and NA formation potential(FP) in source water.Besides, the use of ozonation in the DWTP and chloramination in networks will increase the NDMA concentration in tap water.To address these challenges, the biopretreatment was applied in this DWTP to decrease the concentration of ammonium and NAs.The following biological activated carbon(BAC) will neutralize the nitrosamine increase brought by ozonation.The use of free chlorine in disinfection process will also decrease the NDMA formation compared with chloramination.The results will benefit other cities in China and other countries with similar impacted water sources.

Formation and control of nitrogenous DBPs from Western Australian source waters: Investigating the impacts of high nitrogen and bromide concentrations

We studied the formation of four nitrogenous DBPs（N-DBPs） classes（haloacetonitriles,halonitromethanes, haloacetamides, and N-nitrosamines）, as well as trihalomethanes and total organic halogen（TOX）, after chlorination or chloramination of source waters. We also evaluated the relative and additive toxicity of N-DBPs and water treatment options for minimisation of N-DBPs. The formation of halonitromethanes, haloacetamides, and N-nitrosamines was higher after chloramination and positively correlated with dissolved organic nitrogen or total nitrogen. N-DBPs were major contributors to the toxicity of both chlorinated and chloraminated waters. The strong correlation between bromide concentration and the overall calculated DBP additive toxicity for both chlorinated and chloraminated source waters demonstrated that formation of brominated haloacetonitriles was the main contributor to toxicity. Ozone–biological activated carbon treatment was not effective in removing N-DBP precursors. The occurrence and formation of N-DBPs should be investigated on a case-by-case basis, especially where advanced water treatment processes are being considered to minimise their formation in drinking waters, and where chloramination is used for final disinfection.

Capability of cation exchange technology to remove proven N-nitrosodimethylamine precursors

N-nitrosodimethylamine（NDMA） precursors consist of a positively charged dimethylamine group and a non-polar moiety, which inspired us to develop a targeted cation exchange technology to remove NDMA precursors. In this study, we tested the removal of two representative NDMA precursors, dimethylamine（DMA） and ranitidine（RNTD）, by strong acidic cation exchange resin. The results showed that pH greatly affected the exchange efficiency, with high removal（DMA 〉 78% and RNTD 〉 94%） observed at pH 〈 pk_a-1 when the molar ratio of exchange capacity to precursor was 4. The exchange order was obtained as follows： Ca^（2＋）〉 Mg^（2＋）〉 RNTD~＋〉 K~＋〉 DMA~＋〉 NH_4~＋〉 Na~＋. The partition coefficient of DMA~＋to Na~＋was 1.41 ± 0.26, while that of RNTD~＋to Na~＋was 12.1 ± 1.9. The pseudo second-order equation fitted the cation exchange kinetics well. Bivalent inorganic cations such as Ca^（2＋）were found to have a notable effect on NA precursor removal in softening column test. Besides DMA and RNTD, cation exchange process also worked well for removing other 7 model NDMA precursors. Overall, NDMA precursor removal can be an added benefit of making use of cation exchange water softening processes.