Concentrations Of N-nitrosamines Research Articles

Occurrence and Risk Assessment of N-nitrosamines and Their Precursors in Qingjiang River Basin

N-nitrosamines are a type of nitrogen-containing organic pollutant with high carcinogenicity and mutagenicity. In the main drinking water sources of small and medium-sized towns in China, the contamination levels of N-nitrosamines remain unclear. In addition, there is still lack of research on the concentration of N-nitrosamines and their precursors in tributary rivers. In this study, eight N-nitrosamines and their formation potentials （FPs） were investigated in the Qingjiang River, which is a primary tributary of the Yangtze River. The sewage discharge sites were also monitored, and the environmental influencing factors, carcinogenic and ecological risks caused by N-nitrosamines, and their precursors were evaluated. The results showed that six N-nitrosamines were detected in water samples of the Qingjiang River, among which NDMA [（10 ±15） ng·L-1], NDEA [（9.3 ±9.3） ng·L-1], and NDBA [（14 ±7.8） ng·L-1] were the dominant N-nitrosamines, whereas seven N-nitrosamines were detected in chloraminated water samples, among which NDMA-FP [（46 ±21） ng·L-1], NDEA-FP [（26 ±8.3） ng·L-1], and NDBA-FP [（22 ±13） ng·L-1] were the dominant N-nitrosamine FPs. The concentrations of N-nitrosamines in the middle reaches of the Qingjiang River were higher than those in the upper and lower reaches. Furthermore, the concentrations of N-nitrosamines in the sample sites of sewage discharge and tributaries were significantly higher than those in other sampling sites. The monitoring results at the direct sewage discharge points indicated that the main source of N-nitrosamines in river water was the sewage carrying N-nitrosamines and their precursors. In addition, the concentrations of the three dominant N-nitrosamines including NDMA, NDBA, and NDEA were positively correlated with each other, mainly because of their similar sewage sources. The average carcinogenic risk to residents due to N-nitrosamine in drinking water sources was 2.4×10-5, indicating a potential carcinogenic risk. Moreover, due to the high concentrations of N-nitrosamine formation potentials in the Qingjiang River, the carcinogenic risk of drinking water may be even higher. The ecological risk assessment showed that the ecological risk quotient values of N-nitrosamines in the Qingjiang River watershed were lower than 0.002, which was negligible.

Industrial effluents and N-nitrosamines in karst aquatic systems: a study on distribution and ecological implications.

The discharge of electroplating wastewater, containing high concentrations of N-nitrosamines, poses significant risks to human health and aquatic ecosystems. Karst aquatic environment is easily impacted by N-nitrosamines due to the fragile surface ecosystem. However, it's still unclear in understanding N-nitrosamine transformation in karst water systems. To explore the response and transport of nine N-nitrosamines in electroplating effluent within both karst surface water and groundwater, different river and groundwater samples were collected from both the upper and lower reaches of the effluent discharge areas in a typical karst industrial catchment in Southwest China. Results showed that the total average concentrations of N-nitrosamines (∑NAs) in electroplating effluent (1800ng/L) was significantly higher than that in the receiving river water (130ng/L) and groundwater (70ng/L). The dynamic nature of karst aquifers resulted in comparable average concentrations of ∑NAs in groundwater (70ng/L) and river water (79ng/L) at this catchment. Based on the principal component analysis and multiple linear regression analysis, the electroplating effluent contributed 89% and 53% of N-nitrosamines to the river water and groundwater, respectively. The results based on the species sensitivity distribution model revealed N-nitrosodibutylamine as a particularly toxic compound to aquatic organisms. Furthermore, the average N-nitrosamine carcinogenic risk was significantly higher in lower groundwater reaches compared to upper reaches. This study represents a pioneering effort in considering specific N-nitrosamine properties in evaluating their toxicity and constructing species sensitivity curves. It underscores the significance of electroplating effluent as a primary N-nitrosamine source in aquatic environments, emphasizing their swift dissemination and significant accumulation in karst groundwater.

N-nitrosamines in electroplating and printing/dyeing industrial wastewater treatment plants: Removal efficiency, environmental emission, and the influence on drinking water

The discharge of industrial wastewater containing high concentrations of N-nitrosamines to the aquatic environment can impair downstream source waters and pose potential risks to human health. However, the transport and fate of N-nitrosamines in typical industrial wastewater treatment plants (IWWTPs) and the influence of these effluents on source water and drinking water are still unclear. This study investigated nine N-nitrosamines in four full-scale electroplating (E-) and printing/dyeing (PD-) IWWTPs, two drinking water treatment plants (DWTPs) in the lower reaches of these IWWTPs, and the corresponding tap water in South China. The total concentrations of N-nitrosamines (∑NAs) were 382–10,600, 480–1920, 494–789, and 27.9–427 ng/L in influents, effluents, source water, and tap water, respectively. The compositions of N-nitrosamine species in different influents varied a lot, while N-nitrosodi-n-butylamine (NDBA) and N-nitrosodimethylamine (NDMA) dominated in most of the effluents, source water, and tap water. More than 70 % N-nitrosamines were removed by wastewater treatment processes used in E-IWWTPs such as ferric-carbon micro-electrolysis (Fe/C-ME), while only about 50 % of N-nitrosamines were removed in PD-IWWTPs due to the use of chlorine reagent or other inefficient conventional processes such as flocculation by cationic amine-based polymers or bio-contact oxidation. Therefore, the mass fluxes of N-nitrosamines discharged from these industrial wastewaters to the environment in the selected two industrial towns were up to 14,700 mg/day. The results based on correlation and principal component analysis significantly demonstrated correlations between E-and PD-effluents and source water and tap water, suggesting that these effluents can serve as sources of N-nitrosamines to local drinking water systems. This study suggests that N-nitrosamines are prevalent in typical IWWTPs, which may infect drinking water systems. The findings of this study provide a basis data for the scientific evaluation of environmental processes of N-nitrosamines.

Immunological and genetic profile of the pediatric population in the nitrate geochemical province

BACKGROUND: Contamination of groundwater with nitrates may result in substantial adverse effects on the health of various population groups.
 AIM: To study the immune status and genetic profile of children residing in the nitrate geochemical province in the Perm Region.
 MATERIAL AND METHODS: We conducted a study on a total of 78 preschool children residing in areas with varying levels of nitrate in the underground drinking water sources. The children were divided into two groups for comparison purposes. The first group consisted of 43 children who consumed drinking water that met the acceptable standards for nitrate content. The second group comprised 35 children who consumed drinking water with elevated levels of nitrates. To assess the impact of nitrate content on the children’s health, several measurements were taken. Firstly, the level of nitrates in the household drinking water was analyzed. Additionally, the concentration of N-nitrosamines and nitrate ions in the children’s urine, was determined. To evaluate the immunoregulation parameters, the technology of flow cytometry and enzyme immunoassay were employed, along with PCR to examine genetic polymorphisms.
 RESULTS: A statistically significant difference (p 0.001) was observed in the nitrate content of drinking water between the observation area and the comparison area, with the former showing levels 2.8 times higher. Furthermore, children in the observation group exhibited a significant increase (p 0.05) of 2.3 times in N-nitrosodiethylamine content and 1.6 times in nitrate ion concentration in their urine compared to children in the comparison group. In addition, the observation group displayed a significant decrease (p 0.05) in the number of NKT cells and an increase in the levels of CD3+CD25+-, CD3+CD95+-cells, bax, IL-17, Annexin V-FITC+PI–-, and Annexin V-FITC+PI+-lymphocytes, when compared to the results obtained from the comparison group. Moreover, the presence of polymorphisms in candidate genes associated with tumor formation (CYP1A1 (rs1048943), MMP9 (rs17576), PPARD (rs2016520), BRCA1 G/A (rs3950989)) was also identified.
 CONCLUSION: Our results suggest that children who are exposed to chronic low-levels of nitrates (at a concentration of 1.2 MPC) through drinking water from underground sources exhibit an excessive presence of N-nitrosodiethylamine and nitrate ions in their urine. These findings, in conjunction with the genetic profile of genes responsible for tumor formation, influences the characteristics of the immune response.

Occurrence and mass loads of N-nitrosamines discharged from different anthropogenic activities in Desheng River, South China

N-nitrosamines are widespread in various bodies of water, which is of great concern due to their carcinogenic risks and harmful mutagenic effects. Livestock rearing, domestic, agricultural, and industrial wastewaters are the main sources of N-nitrosamines in environmental water. However, information on the amount of N-nitrosamines these different wastewaters contribute to environmental water is scarce. Here, we investigated eight N-nitrosamines and assessed their mass loadings in the Desheng River to quantify the contributions discharged from different anthropogenic activities. N-nitrosodimethylamine (NDMA) (< 1.6-18ng/L), N-nitrosomethylethylamine (NMEA) (< 2.2ng/L), N-nitrosodiethylamine (NDEA) (< 1.7-2.4ng/L), N-nitrosopyrrolidine (NPYR) (< 1.8-18ng/L), N-nitrosomorpholine (NMOR) (< 2.0-3.5ng/L), N-nitrosopiperidine (NPIP) (< 2.2-2.5ng/L), and N-nitrosodi-n-butylamine (NDBA) (< 3.3-16ng/L) were detected. NDMA and NDBA were the dominant compounds contributing 89% and 92% to the total N-nitrosamine concentrations. The mean cumulative concentrations of N-nitrosamines in the livestock rearing area (26 ± 11ng/L) and industrial area (24 ± 4.8ng/L) were higher than those in the residential area (16 ± 6.3ng/L) and farmland area (15 ± 5.1ng/L). The mean concentration of N-nitrosamines in the tributaries (22ng/L) was slightly higher than that in the mainstem (17ng/L), probably due to the dilution effect of the mainstem. However, the mass loading assessment based on the river's flow and water concentrations suggested the negligible mass emission of N-nitrosamines into the mainstem from tributaries, which could be due to the small water flow of tributaries. The average mass loads of N-nitrosamines discharged into the mainstem were ranked as the livestock rearing area (742.7g/d), industrial area (558.6g/d), farmland area (93.9g/d), and residential areas (83.2g/d). In the livestock rearing, residential, and industrial area, NDMA (60.9%, 53.6%, and 46.7%) and NDBA (34.6%, 33.3%, and 44.9%) contributed the most mass loads; NDMA (23.4%), NDEA (15.8%), NPYR (10.1%), NPIP (12.8%), and NDBA (37.8%) contributed almost all the mass loads in the farmland area. Photodegradation amounts of NDMA (0.65 ~ 5.25µg/(m3·day)), NDBA (0.37 ~ 0.91µg/(m3·day)), and NDEA (0 ~ 0.66µg/(m3·day)) were also calculated according to the mass loading. Quantifying the contribution of different anthropogenic activities to the river will provide important information for regional river water quality protection. Risk quotient (RQ) values showed the negligible ecological risks for fish, daphnid, and green algae.

A survey of industrial N-nitrosamine discharges in Switzerland

N-nitrosamines are formed during different industrial processes and are of significant concern due to their carcinogenic and mutagenic properties. This study reports concentrations of N-nitrosamines in eight different industrial wastewater treatment plants in Switzerland and the variability of their abundance. Only four N-nitrosamines species, N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine (NDEA), N-nitrosodibutylamine (NDPA) and N-nitrosomorpholine (NMOR) were above the limit of quantification in this campaign. Remarkably high concentrations (i.e. up to 975 μg NDMA/L, 90.7 μg NDEA/L, 1.6 μg NDPA/L and 710 μg NMOR/L) of these N-nitrosamines were detected at seven of eight sites. These concentrations are two to five orders of magnitude higher than those typically detected in municipal wastewater effluents. These results suggest that industrial effluents may be a major source of N-nitrosamines. Although very high concentrations of N-nitrosamine have been detected in industrial discharges, various processes in surface water can partially mitigate their concentrations (e.g. photolysis, biodegradation and volatilization) and hence the risk to human health and aquatic ecosystems. Nevertheless, there is little information on long-term effects on aquatic organisms and therefore the discharge of N-nitrosamines to the environment should be avoided until the impact on ecosystems is assessed. During winter a less efficient mitigation of N-nitrosamines can be expected (lower biological activity, less sunlight) and therefore, emphasis should be put on this season in future risk assessment studies.

Relating algal-derived extracellular and intracellular dissolved organic nitrogen with nitrogenous disinfection by-product formation

The dissolved organic nitrogen (DON) pool from algal-derived extracellular and intracellular organic matter (EOM and IOM) comprises proteins, peptides, free amino acids and carbohydrates, of which, proteins can contribute up to 100% of the DON. Previous reports of algal-derived DON character have focused on bulk properties including concentration, molecular weight and hydrophobicity. However, these can be similar between algal species and between the EOM and IOM even when the inherent molecular structures vary. A focus on bulk character presents challenges to the research on algal-derived nitrogenous-disinfection by-product (N-DBP) formation as N-DBP formation is sensitive to the changes in molecular structure. Hence, the main aim of this study was to characterize algal EOM and IOM-derived DON, specifically proteinaceous-DON, using a combination of bulk and molecular characterization techniques to enable a more detailed exploration of the relationship between the character of algal-derived proteins and the N-DBP formation potential. DON from the EOM and IOM of four commonly found algae and cyanobacteria in natural waters were evaluated, namely Chlorella vulgaris, Microcystis aeruginosa, Dolichospermum circinale, and Cylindrospermopsis raciborskii. It was observed that 77-96% of total DON in all EOM and IOM samples was of proteinaceous origin. In the proteins, DON concentrations were highest in the high molecular weight fraction of IOM-derived bulk proteins (0.13–0.75 mg N L−1) and low to medium molecular weight fraction of EOM-derived bulk proteins (0.15–0.63 mg N L−1) in all species. Similar observations were also made via sodium dodecyl sulphate polyacrylamide gel electrophoresis and liquid chromatography-high resolution mass spectrometry. Solid-state 15N nuclear magnetic resonance (NMR) spectroscopy of the EOM and IOM revealed the existence of common aliphatic and heterocyclic N-groups in all samples, including a dominant 2° amide peak. Species dependent variability was also observed in the spectra, particularly in the EOM; e.g. nitro signals were found only in the Cylindrospermopsis raciborskii EOM. Dichloroacetonitrile (DCAN) and N-nitrosamine concentrations from the EOM of the species evaluated in this study were lower than the guideline limits set by regulatory agencies. It is proposed that the dominant 2° amide in all samples decreased N-DBP formation upon chlorination. For chloramination, the presence of nitro groups and aliphatic and heterocyclic N-DBP precursors could cause variable N-nitrosamine formation. Compared to non-algal impacted waters, algae-laden waters are characterised by low organic carbon: organic nitrogen ratios of ∼7–14 and elevated DON and protein concentrations. Hence, relying only on bulk characterization increases the perceived risk of N-DBP formation from algae-laden waters.

Fluorescent paper-based sensor integrated with headspace thin-film microextraction for the detection of acyclic N-nitrosamines following in situ photocatalytic decomposition

BackgroundIn this work, a novel analytical approach based on the photocatalytic decomposition of N-nitrosamines combined with headspace thin-film microextraction of the generated nitrogen oxides such as NO has been developed for the determination of the acyclic N-nitrosamine fraction in drinking water samples. A hydrophilic cellulose substrate modified with fluorescent silver nanoclusters (Ag NCs) was used both as extractant and sensing platform. A quenching effect of Ag NCs fluorescence occurs as the concentration of N-nitrosamines increases. Front-face fluorescence spectroscopy with a solid sample holder was employed for directly measuring the fluorescence quenching onto the cellulose substrate. ResultsIn order to achieve an optimal analytical response, different parameters involved in the photocatalytic reaction as well as those concerning the microextraction step were fully investigated. It is demonstrated that the photodegradation rate of cyclic N-nitrosamines at acidic pH is much lower than that of acyclic ones, which can be the basis for the determination of the later fraction in waters. Under optimal conditions, a detection limit for the acyclic N-nitrosamine fraction around 0.08 μg L−1 using N-nitrosodimethylamine (NDMA) as model compound for calibration was obtained. Several drinking waters were spiked with acyclic N-nitrosamines showing recoveries in the range of 98–102% with a relative standard deviation of 3–4% (N = 3). Significance and noveltyN-nitrosamines generated as by-products during disinfection processes applied to water cause multiple adverse effects on human health being classified as potential human carcinogens.This study highlights the suitability of a fluorescent paper-based sensor for the rapid analysis of the acyclic N-nitrosamine fraction (i.e. the most abundant fraction) as a total index in drinking water, being useful as screening tool before exhaustive chromatographic analysis, which saves costs, time and reduces waste generation.

Characteristics and health risk assessment of volatile N-nitrosamines in the plasma of adults in Guangdong Province, China

N-nitrosamines are strong carcinogens that are widely present in the environment. This study developed a method, and analyzed the concentrations of volatile N-nitrosamines (VNAs) in the plasma of adults in Guangdong Province, China. Finally, the health risks to adults in Guangdong Province, China, with dietary exposure to VNAs were assessed. Gas chromatography/mass spectrometry (GC/MS) in electron impact (EI) ionization source mode was used to quantitatively analyze VNAs, and to perform accurate mass determination. The lower limit of detection (LOD) of nine nitrosamines are ranged from 0.01 to 2.14 ng/mL. The recovery rate ranged from 83 % to 116 %, and the relative standard deviation (RSD) was < 10 %. The method developed is simple, rapid, and provides good reproducibility and high sensitivity. N-nitrosodimethylamine (NDMA), N-nitrosomethylethylamine (NMEA), N-nitrosodinbutylamine (NDBA), N-nitrosopiperidine (NPIP), N-nitrosopyrrolidine (NPYR), N-nitrosomorpholine (NMOR) and N-nitrosodiphenylamine (NDPhA) were detected in 92 adult plasma samples. NDMA and NMEA were detected in 56.5 % and 44.6 % of the samples, followed by NPIP (34.8 %). NDMA had the highest median concentration (43.7 ng/mL) in the total samples. There were gender-related differences found in the concentrations of NDBA and NDPhA. The exposure risk assessment results showed that the two highest daily dietary intakes of VNAs were N-nitrosodi-n-propylamine (NDPA) and NDMA, and aquatic products and pickled vegetables contributed the most total nitrosamine intake. The lifetime cancer risk of adults ranged from 2.88 × 10−10 to 7.46 × 10−5, and the risk associated with NDMA, NDPA, N-nitrosodiethylamine (NDEA), NMEA and NPIP are important and should attract more attention. This study aimed to explore the exposure levels of VNAs in the plasma of adults in Guangdong Province, China, and to assess the health risks of dietary intake of VNAs, which provides a basis of the effect of VNAs exposure on human health.

Seasonal variability, predictive modeling and health risks of N-nitrosamines in drinking water of Shanghai

The prevalence of carcinogenic N-nitrosamines in drinking water is of significant concern. In the present study, eight N-nitrosamines from three representative drinking water treatment plants (DWTPs) in Shanghai, China were monitored for an entire year to evaluate their seasonal variability, probabilistic cancer risk and the resulting disease burden. The possibility of employing routinely monitored water quality parameters as predictors of N-nitrosamines was also examined. The results showed that the Taipu River-fed reservoir suffered more serious N-nitrosamine contamination than the Yangtze River-fed reservoirs. Winter witnessed higher levels of N-nitrosamines in both source and finished water. N-nitrosamine concentrations increased from source water to finished water in autumn or winter, but no spatial variations were observed in summer. The total lifetime cancer risk (LCR) posed by N-nitrosamines in finished water was within the acceptable range (1.00 × 10−6 to 1.00 × 10−4), with N-nitrosodimethylamine (NDMA) and N-nitrosodiethylamine (NDEA) being the main contributors. Winter and autumn were found to have higher total LCR values. The average individual disability-adjusted life years (DALYs) lost was 4.43 × 10−6 per person-year (ppy), exceeding the reference risk level (1.00 × 10−6 ppy). Liver cancer accounted for 97.1 % of the total disease burden, while bladder and esophagus cancers made a little contribution (2.9 %). A multiple regression model was developed to estimate the total N-nitrosamines in finished water as a function of water quality parameters, and the R2 value was 0.735. This study not only provides fundamental data for public health policy development, but also reveals the necessity to incorporate a seasonal control strategy in DWTPs to minimize the associated health risks induced by N-nitrosamines.

Multivariate experimental design provides insights for the optimisation of rechloramination conditions and water age to control disinfectant decay and disinfection by-product formation in treated drinking water

The stability of drinking water disinfectant residuals is known to be influenced by multiple variables. To evaluate the effects of various influencing variables on disinfectant stability, a multivariate analysis of chloramine decay and associated disinfection by-products (DBPs) formation was investigated in a series of bench-scale experiments. Of nine water quality variables previously identified, monochloramine dose, pH, and bromide concentration were selected as key water quality variables based on previous investigations and modelling. Co-effects of these key variables on monochloramine decay and formation of 33 halogenated and nitrogen-containing DBPs were investigated using response surface experimental design.Rechloramination conditions, including monochloramine dose, pH and bromide concentration, were optimised via a 3-factorial multivariate analysis of monochloramine stability in post-treatment drinking water. Effects of influencing variables on disinfectant decay and DBP formation were assessed and graphically presented as response surfaces with minimal experiments using Doehlert matrix experimental design compared to other multivariate experimental designs. Concentrations of trihalomethanes (THMs), haloacetic acids (HAAs), and N-nitrosamines were found to increase with water age, whereas opposite phenomenon was observed in the net production of haloacetonitriles (HANs). Increasing pH was found to stabilise monochloramine but it could cause DBP speciation to shift. Furthermore, increasing bromide concentration elevated Br-DBP formation. In bromide-containing water, pH = 7.8–8.0 should be considered as higher pH increases Br-THMs formations and lower pH increases formations of Br-HAAs and Br-HANs. However, water age or pH has insignificant impacts on DBP formation after significant monochloramine decay or at low initial monochloramine dose.These findings indicate that effective combined control measures to maintain monochloramine stability should include the application of high monochloramine dose (>1.5 mg-Cl2.L−1) under conditions of moderate to high pH (pH = 7.8–8.0) and minimal bromide concentration. This study provides relevant insights to water utilities aiming to design effective disinfectant residual management strategies for controlling monochloramine decay and DBP formation.

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Monitoring of the concentration of toxic elements, N-nitrosamines, pesticides, polychlorinated biphenyls and cesium and strontium radionuclides in the raw muscle tissue of the Japanese mackerel putin 2014-2019 was carried out.&#x0D; It was found that the investigated safety indicators of Japanese mackerel caught in the South Kuril fishing zone and in the Pacific subzone of the North Kuril fishing zone in 2014 – 2019 correspond to modern quality requirements. It is noted that Japanese mackerel can be used as a valuable raw material for the production of food products.

Determining the leading sources of N-nitrosamines and dissolved organic matter in four reservoirs in Southern China

The presence of carcinogenic N-nitrosamines and dissolved organic matter (DOM) in freshwater is a significant concern from the perspective of public health and drinking water treatment plant operation. This study investigated the N-nitrosamines concentration and their precursors' distributions, and DOM composition in four reservoirs located in a southern city of China. A total of 22 renowned precursors were identified. Precursors from industrial and pharmaceutical origins were found to be dominant in all reservoirs; however, traces of pesticide-based precursors, i.e. pirimicarb and cycluron were also found. The distribution of nine N-nitrosamines was substantially different among the reservoirs. N-Nitrosodibutylamine (NDBA), N-Nitrosopiperidine (NPIP), N-Nitrosodimethylamine (NDMA), and N-Nitrosopyrrolidine (NPYR) were abundantly present in all reservoirs. Most of N-nitrosamines except NDMA and N-nitrosodiethylamine (NDEA) were far below the generally accepted cancer risk of 10−6, and NDMA/NDEA were found close to the risk level (10−6). Anthropogenic DOM was dominant in three reservoirs as depicted by a higher biological index (BIX) than the humification index (HIX). By the principle component analysis, BIX appeared as an indicator of N-nitrosamines (except NDEA and NPIP). A strong and direct relationship was observed between the NDMA-formation potential (FP) and concentration of total N-nitrosamines (∑NA), and BIX. These results confirmed that the anthropogenic activities were the leading source of DOM and N-nitrosamines in this city based on land-use.

Trace-level quantification of N-nitrosopiperazine in treated wastewater using supported liquid extraction and hydrophilic interaction chromatography mass spectrometry

Regenerable amine-based solvents used for post-combustion CO2 capture, primarily monoethanolamine and piperazine, are known to undergo degradation and secondary reactions over time forming, amongst other species, N-nitrosamines. These carcinogenic species can eventually make their way from treated wastewater into environmental waters. The United States Environmental Protection Agency (US EPA) recommends that the concentration of N-nitrosamines in surface water not exceed 1.24 μg/L. We have developed a straightforward method to quantify N-nitrosopiperazine in treated wastewater by hydrophilic interaction liquid chromatography – mass spectrometry (HILIC–MS) after sample preparation by supported liquid extraction (SLE). To achieve the best extraction recovery and method limits of quantification (MLOQ), standards were prepared in a high-salt synthetic matrix to mimic the treated wastewater effluent. To further improve the MLOQ, the drying steps after extraction were optimized. HILIC separation of the highly polar analytes was achieved using an ethylene-bridged hybrid amide stationary phase. Detection was achieved using a triple quadrupole mass spectrometer operated in positive electrospray ionisation and multiple reaction monitoring mode, providing a final MLOQ of 0.25 μg/L for N-nitrosopiperazine. Validation of the method was carried out to ensure good confidence in the data obtained for a treated wastewater sample from a post-combustion CO2 capture facility. In addition, N-nitrosopiperazine was quantified with the developed SLE-HILIC–MS method in eight degraded carbon capture samples that had not yet undergone wastewater treatment.

Contamination, Decomposition, and Formation of N-Nitrosodimethylamine in Water Samples at the ng/L Level of Determination.

An ultra-sensitive analytical system that can determine the concentration of N-nitrosamines at the ng/L level without preconcentration was used to investigate the contamination, decomposition, and formation of N-nitrosodimethylamine (NDMA) and other N-nitrosamines in water samples during general analytical procedures. A preliminary experiment was performed to estimate the NDMA concentrations in ambient air. Since the air samples contained NDMA at concentrations in the range of 2.0 - 10.7 ng/m3, ambient air was identified as the source of NDMA contamination in water samples. We directly confirmed that the concentration of aqueous 10-ng/L NDMA samples stored in clear glass bottles decreased upon exposure to sunlight. Thus, to maintain the N-nitrosamine concentration, such samples must always be protected from sunlight during sampling. The existence of N-nitrosamines in experimental reagents, such as ranitidine and sodium hypochlorite solutions, was also confirmed, as was the formation of NDMA on an activated carbon solid-phase extraction cartridge.

Concentration of N-Nitrosamines in condoms purchased in Korea

TPS 624: Exposures to pops, voc and other chemicals, Johan Friso Foyer, Floor 1, August 26, 2019, 3:00 PM - 4:30 PM N-Nitrosamines are the nitroso-compounds which are produced by nitrosation reactions of the secondary amine and nitrite. N-Nitrosamine has been found to be produced through the vulcanization process during the production of rubber products. Recently, nitrosamines have been detected in rubber products and become a major topic. Condoms are disposable medical devices, so safety is important because they come into direct contact with the skin and mucous membranes. In this study, we modified an analysis of nitrosamines in the condoms of 2016, which was created by applying the ISO 29941 method. The samples were eluted by distilled water, and target compounds were extracted by liquid-liquid extraction with dichloromethane. And then after concentrated, and quantitatively analyzed by LC-MS/MS. Validation was performed prior to analyzing the samples. The accuracies of the analytical method were ranged from 87.4 to 112.2%, precisions were lower than 10.7%, and the detection limits were from 0.16 (NDPA) to 0.81 (NDELA) ng/mL. In this study, 190 condoms distributed in Korea were analyzed. Interestingly, different types of nitrosamines were found in different samples of companies. NDBA was detected in all samples. The concentrations of nitrosamine in the condoms were NDMA: ND~8.1ng/g, NDEA: ND~144.2ng/g, NDBA: ND~161.5ng/g NDELA: ND~17.9ng/g. Of the 190 samples, NDMA were detected from 6 case, NDEA from 88 cases, NDBA from 184 cases and NDELA from 11 cases. There were no significant differences in the concentrations of the samples in the same LOT number, but the sample concentrations were different when the LOT numbers were different. The concentration was lowered as it was washed several times. Nitrosamines are detected in condoms distributed in Korea, and various kinds of vulcanizing agents are used by companies, so that various types of nitrosamines are detected. Because nitrosamines are highly hydrophilic, fewer nitrosamines were detected when the condom was washed multiple times.

Rapid Identification and Determination of N-Nitrosamines in Food Products by Ultra-High-Performance Liquid Chromatography–High Resolution Quadrupole-Time-of-Flight Mass Spectrometry by Exact Masses of Protonated Molecules

A method is proposed for the rapid identification and determination of seven N-nitrosamines in food products by ultra-high-performance liquid chromatography in combination with high-resolution quadrupole-time-of-flight mass spectrometry. The ranges of detectable concentrations of N-nitrosamines are from 0.001–5 to 2–100 ng/mL for liquid (water, beer) and from 2–50 to 4–100 ng/g for solid (meat, fish, mussels, malt, grain, sausage, wieners, and bockwursts) products. The limits of detection are 0.0005–2 ng/mL, 2–5 ng/g for liquid and solid products, respectively. The recovery of analytes is from 62 to 105%. The matrix effect was estimated in determining N-nitrosamines in samples of different nature. The matrix effect is negligible (≤20%) in the determination of N-nitrosamines in water and is significant for beer, meat products, grain, malt, and fish (>20%). A procedure is proposed for the rapid identification and determination of N-nitrosamines by the standard addition method and using matrix calibration. The relative standard deviation of the results of analysis does not exceed 17%. The duration of sample identification is 40 min; the determination of the detected analytes takes 1–1.5 h.

Role of various factors affecting the photochemical treatment of N-nitrosamines related to CO2 capture

ABSTRACT Post-combustion CO2 capture using amine solvents is the most feasible method of reducing anthropogenic CO2 emissions, which are the largest contributor to global warming. The formation of carcinogenic N-nitrosamines (i.e. by-products) can hinder the industrial application of this technology. In this study, the effects of direct UV photolysis (N-nitrosamine concentration and amines) and advanced oxidation processes (UV/H2O2 and UV/O3) on the three specific N-nitrosamines that are commonplace in amine-based CO2 capture (i.e. N-nitrosodiethylamine (NDEA), N-nitrosodiethanolamine (NDELA), and N-nitrosomorpholine (NMOR)) were examined. A significant decrease in the photodegradation rate constants was observed for NDEA (1.02 × 100 to 2.94 × 10−1 min−1), NDELA (1.52 × 100 to 3.32 × 10−1 min−1), and NMOR (1.93 × 100 to 2.20 × 10−1 min−1) as their concentrations increased within 1–50 mg/L. This is the first report of a significant increase in the degradation rate constants of N-nitrosamine with an increase in amine concentrations (i.e. monoethanolamine, diethanolamine, and morpholine) within 10–200 mM. The photodegradation rate constants increased as the molar ratio of H2O2 to N-nitrosamine increased to 20, but then decreased at molar ratios beyond this. O3 had a negligible effect on the photodegradation of N-nitrosamines.

Pharmacological preconditioning with inhaled nitric oxide (NO): Organ-specific differences in the lifetime of blood and tissue NO metabolites

BackgroundEndogenous nitric oxide (NO) may contribute to ischemic and anesthetic preconditioning while exogenous NO protects against ischemia-reperfusion (I/R) injury in the heart and other organs. Why those beneficial effects observed in animal models do not always translate into clinical effectiveness remains unclear. To mitigate reperfusion damage a source of NO is required. NO inhalation is known to increase tissue NO metabolites, but little information exists about the lifetime of these species. We therefore sought to investigate the fate of major NO metabolite classes following NO inhalation in mice in vivo. MethodsC57BL/6J mice were exposed to 80 ppm NO for 1 h. NO metabolites were measured in blood (plasma and erythrocytes) and tissues (heart, liver, lung, kidney and brain) immediately after NO exposure and up to 48 h thereafter. Concentrations of S-nitrosothiols, N-nitrosamines and NO-heme products as well as nitrite and nitrate were quantified by gas-phase chemiluminescence and ion chromatography. In separate experiments, mice breathed 80 ppm NO for 1 h prior to cardiac I/R injury (induced by coronary arterial ligation for 1 h, followed by recovery). After sacrifice, the size of the myocardial infarction (MI) and the area at risk (AAR) were measured. ResultsAfter NO inhalation, elevated nitroso/nitrosyl levels returned to baseline over the next 24 h, with distinct multi-phasic decay profiles in each compartment. S/N-nitroso compounds and NO-hemoglobin in blood decreased exponentially, but remained above baseline for up to 30min, whereas nitrate was elevated for up to 3hrs after discontinuing NO breathing. Hepatic S/N-nitroso species concentrations remained steady for 30min before dropping exponentially. Nitrate only rose in blood, liver and kidney; nitrite tended to be lower in all organs immediately after NO inhalation but fluctuated considerably in concentration thereafter. NO inhalation before myocardial ischemia decreased the ratio of MI/AAR by 30% vs controls (p = 0.002); only cardiac S-nitrosothiols and NO-hemes were elevated at time of reperfusion onset. ConclusionsMetabolites in blood do not reflect NO metabolite status of any organ. Although NO is rapidly inactivated by hemoglobin-mediated oxidation in the circulation, long-lived tissue metabolites may account for the myocardial preconditioning effects of inhaled NO. NO inhalation may afford similar protection in other organs.

Risk assessment of N-nitrosodiethylamine (NDEA) and N-nitrosodiethanolamine (NDELA) in cosmetics

ABSTRACTN-nitrosamines and their precursors found in cosmetics may be carcinogenic in humans. Thus the aim of this study was to carry out risk assessment for N-nitrosamines (N-nitrosodiethanolamine [NDELA], N-nitrosodiethylamine [NDEA]) and amines (triethanolamine [TEA], diethanolamine [DEA]) levels in cosmetics determined using validated liquid chromatography–tandem mass spectrometry (LC–MS/MS) procedures. NDELA and NDEA concentrations were present at levels of “not detected” (N.D.) to 596.5 μg/kg and N.D. to 40.9 μg/kg, respectively. TEA and DEA concentrations ranged from N.D. to 860 μg/kg and N.D. to 26.22 μg/kg, respectively. The nitrite concentration (3–2250 mg/l), number of nitrosating agents to a maximum 5, and pH (3.93–10.09) were also assessed. The impact of N-nitrosamine formation on the levels of TEA, DEA, nitrite, and other nitrosating agents was also examined. N-nitrosamine concentrations correlated with the number of nitrosating agents and nitrite concentrations. Data demonstrated that higher nitrite concentrations and a greater number of nitrosating agents increased NDELA and NDEA yields. Further, the presence of TEA and DEA exerted a significant influence on N-nitrosamine formation. Risk assessments, including the margin of exposure (MOE) and lifetime cancer risk (LCR) for N-nitrosamines and margin of safety (MOS) for amines, were calculated using product type, use pattern, and concentrations. Exposure to maximum amounts of NDELA and NDEA resulted in MOE > 10,000 (based upon the benchmark dose lower confidence limit 10%) and LCR <1 × 10−5, respectively. In addition, TEA and DEA concentrations in cosmetic samples resulted in MOS values >100. Therefore, no apparent safety concerns were associated with cosmetic products containing NDELA, NDEA, TEA, and DEA in this study. However, since amines and nitrosating agents produce carcinogenic nitrosamines, their use in cosmetics needs to be minimized to levels as low as technically feasible.