N-nitrosodimethylamine Precursors Research Articles

Animal Feedlots and Domestic Wastewater Discharges are Likely Sources of N-Nitrosodimethylamine (NDMA) Precursors in Midwestern Watersheds.

N-nitrosodimethylamine (NDMA) precursor concentrations along four major rivers in Minnesota, USA were quantified and correlated with watershed land cover types, anthropogenic activity, and organic matter characteristics. River water samples (36 in total) were chloraminated under uniform formation conditions (UFC) before and after lime-softening treatment, and the resulting NDMA concentrations were quantified (NDMAUFC). Regarding land cover, NDMAUFC in raw river water exhibited weak positive correlations with urban land (ρ = 0.33, p = 0.05) and cropland coverage (ρ = 0.35, p = 0.04). For anthropogenic activity, NDMAUFC in raw river water positively correlated with the number of feedlots (ρ = 0.57), total weight of animals (ρ = 0.68), and total number of domestic wastewater treatment plants (WWTPs; ρ = 0.63) with p < 0.01. NDMAUFC positively correlated with region IV fluorescence intensity from fluorescence excitation-emission spectra (ρ = 0.70, p < 0.01). Lime softening of river water typically increased NDMAUFC and preferentially removed organic matter that fluoresces in region V, suggesting that the organic matter in this region decreases NDMAUFC by competing for available chloramines. Overall, animal feedlots, along with domestic WWTPs, are predominant sources of NDMA precursors in the studied watersheds, while croplands and urban runoff are of lesser importance.

Adsorption of typical NDMA precursors by superfine powdered activated carbon: Critical role of particle size reduction

Control of N-nitrosodimethylamine (NDMA) in drinking water could be achieved by removing its precursors as one practical way. Herein, superfine powdered activated carbons with a diameter of about 1 µm (SPACs) were successfully prepared by grinding powdered activated carbon (PAC, D50=24.3 µm) and applied to remove model NDMA precursors, i.e. ranitidine (RAN) and nizatidine (NIZ). Results from grain diameter experiments demonstrated that the absorption velocity increased dramatically with decreasing particle size, and the maximum increase in k2 was 26.8-folds for RAN and 33.4-folds for NIZ. Moreover, kinetic experiments explained that rapid absorption could be attributed to the acceleration of intraparticle diffusion due to the shortening of the diffusion path. Furthermore, performance comparison experiments suggested that the removal of RAN and NIZ (C0=0.5 mg/L) could reach 61.3% and 60%, respectively, within 5 min, when the dosage of SAPC-1.1 (D50=1.1 µm) was merely 5 mg/L, while PAC-24.3 could only eliminate 17.5% and 18.6%. The adsorption isotherm was well defined by Langmuir isotherm model, indicating that the adsorption of RAN/NIZ was a monolayer coverage process. The adsorption of RAN or NIZ by SAPC-1.1 and PAC-24.3 was strongly pH dependent, and high adsorption capacity could be observed under the condition of pH > pka+1. The coexistence of humic acid (HA) had no significant effect on the adsorption performance because RAN/NIZ may be coupled with HA and removed simultaneously. The coexistence of anions had little effect on the adsorption also. This study is expected to provide an alternative strategy for drinking water safety triggered by NDMA.

Spatiotemporal Variability in N-Nitrosodimethylamine Precursor Levels in a Watershed Impacted by Agricultural Activities and Municipal Wastewater Discharges and Effects of Lime Softening.

The Crow River, a tributary of the Mississippi River in Minnesota, U.S.A., that is impacted by agricultural activities and municipal wastewater discharges, was sampled approximately monthly at 12 locations over 18 months to investigate temporal and spatial variations in N-nitrosodimethylamine (NDMA) precursor levels. NDMA precursors were quantified primarily by measuring NDMA formed under the low chloramine dose uniform formation conditions protocol (NDMAUFC) and occasionally using the high dose formation potential protocol (NDMAFP). Raw water NDMAUFC concentrations (2.2 to 128 ng/L) exhibited substantial temporal variation but relatively little spatial variation. An increase in NDMAUFC was observed for 126 of 169 water samples after lime-softening treatment. A kinetic model indicates that under chloramine-limited UFC test conditions, the increase in NDMAUFC can be attributed to a decrease in competition between precursors and natural organic matter (NOM) for chloramines and reduced interactions of precursors with NOM. NDMAUFC concentrations correlated positively with dissolved nitrogen concentration (ρ = 0.44, p < 0.01) when excluding the spring snowmelt period and negatively correlated with dissolved organic carbon concentration (ρ = -0.47, p < 0.01). Overall, NDMA precursor levels were highly dynamic and strongly affected by lime-softening treatment.

Dissolved organic nitrogen removal and its mechanisms during simulated soil aquifer treatment

Soil aquifer treatment systems are known to further remove contaminants in wastewater effluent when applied through infiltration into the ground. Dissolved organic nitrogen (DON) in the effluent, a precursor for nitrogenous disinfection by-products (DBPs) such as N-nitrosodimethylamine (NDMA), is of great concern upon subsequent use of the groundwater infiltered into the aquifer. In this study, the vadose zone of the soil aquifer treatment system was simulated using 1 m laboratory soil columns under unsaturated conditions representing the vadose zone. The final effluent of a water reclamation facility (WRF) was applied to these columns to investigate the removal of N species with a focus on DON, as well as NDMA precursors. DON removal achieved was up to 99 % with an average of 68 % and was accompanied by a 52 % nitrate increase suggesting the occurrence of ammonification and nitrification through the soil columns. Around 62 % of total DON removal was seen at <10 cm travel distance, which was in accordance with higher adenosine triphosphate (ATP) concentrations at the top of the column due to more oxygen and organic matter availability. Total Dissolved N removal was drastically lowered to 4.5 % in the same column without microbial growth, which highlights the importance of biodegradation. The columns were capable of removing 56 % of the fluorescent dissolved organic matter (FDOM). Soil columns could remove NDMA precursors up to 92 % through the column with the initial concentration of 89.5 ng/L, possibly due to the removal of DON fractions. The results demonstrate the capability of the vadose zone in further treatment of DON and other organic matter before reaching the groundwater through infiltration or indirect discharge to surface water. Differences in applied water quality and the site-specific oxic conditions in SAT systems could lead to variable removal efficiencies.

N-Nitrosamines and their precursors in wastewater effluents from selected industries in Spain

N-nitrosamines (NAs), and N-nitrosodimethylamine (NDMA) in particular, are hazardous disinfection byproducts (DBPs) relevant when wastewater impacts drinking water sources and, in water reuse practices. Our study investigates the concentrations of NDMA and five additional NAs and their precursors in industrial wastewater effluents. Aiming to identify potential differences between industrial typologies, wastewaters from 38 industries belonging to 11 types of the UN International Standard Industrial Classification of All Economic Activities system (ISIC) were analysed. Results show that the presence of most NAs and their precursors cannot be linked to a specific industry type as these were in general very different within the classes. Nevertheless, N-nitrosomethylethylamine (NMEA) and N-nitrosopiperidine (NPIP) as well as precursors for N-nitrosodiethylamine (NDEA), NPIP and N-nitrosodibuthylamine (NDBA) could be rank with different concentrations between ISIC classes (p-value < 0.05). Specific industrial wastewater with notable high concentrations of NAs and their precursors were identified too. The effluents with the highest concentration of NDMA belong to the ISIC C2011 class (Manufacture of basic chemical), while the effluents with the highest concentration of NDMA precursors were from the ISIC C1511 class (Tanning and dressing of leather; dressing and dyeing of fur). Other relevant NAs found were NDEA in ISIC class B0810 (Quarrying of stone, sand, and clay) and ISIC class C2029 (Manufacture of other chemical products).

Study on characteristic and mechanism involved in the formation of N-nitrosodimethylamine precursors during microbial metabolism of amino acids

Amino acid metabolism by microorganisms is a new but important pathway for the formation of NDMA precursors in water. We investigated the properties of nitrosamine precursors produced through microbial metabolism of amino acids by polarity rapid assessment method and molecular weight fractionation by ultrafiltration method. The PRAM results showed that the positively charged fraction and the non-polar fraction accounted for most (45 %–79 % and 6 %–82 %, respectively) of the NDMA precursors. The MW fractionation results also indicate the dominant precursors had MWs <1 kDa or over 10 kDa. NDMA precursors produced through amino acid metabolism were identified and quantified. Dimethylamine, N-methyl-alanine and alanine methyl ester were produced during the metabolism of alanine and peptone. Together, N-methyl-alanine and dimethylamine averagely contributed 24 % (12 %–44 %) of the NDMA precursors in the alanine medium. The NDMA precursor formation pathway during alanine metabolism involves the methylation of alanine to form N-methyl-alanine and the decomposition of alanine anabolism products to form dimethylamine. Nitrosamine precursors are generally formed through anabolism or methylation, but biogenic amines or NH3 can be produced through catabolism before nitrosamine precursor synthesis. Microbial community analysis was performed and Ralstonia was found to be a likely key genus contributing to NDMA precursor formation during alanine metabolism.

Identification of transformation products during Doxylamine chloramination for NDMA mitigation

ABSTRACT N-nitrosodimethylamine (NDMA) is a disinfection byproduct that forms at the presence of an organic nitrogen precursor. Doxylamine, an antihistaminic pharmaceutical, is a precursor of NDMA and has been shown to form NDMA in the presence of chloramine. In this study, the effect of Doxylamine as an NDMA precursor has been further studied during chloramination. The end product and byproducts during chloramination were investigated using a high-resolution mass spectrometer by taking samples at different time intervals. Results suggest that NDMA is not the only end product forming during chloramination of Doxylamine and several transformation products that do not end up as NDMA may form. A group of these transformation products have been selected based on their relative amounts during chloramination with time and notated as Focus Tentative Transformation Products (FTTPn). The identification of these byproducts will make it easier to study the conditions during chloramination that may favour these ‘known’ transformation products with the use of less sophisticated analytical instruments. Then, it might lead to the establishment of chloramination protocols that will minimise the formation of NDMA from its precursors.

High concentrations of dissolved organic nitrogen and N-nitrosodimethylamine precursors in effluent from biological nutrient removal process with low dissolved oxygen conditions

The presence of dissolved organic nitrogen (DON) in biological nutrient removal (BNR) effluent has led to increased concern about its adverse effects on wastewater discharge and reuse applications. Previous studies have demonstrated efficient biological inorganic nitrogen removal in BNR under low dissolved oxygen (DO) conditions; however, information on DON is scarce. This study investigated low-DO effects on DON and N-nitrosodimethylamine (NDMA) precursor concentrations in BNR effluents. Identical BNR reactors consisting of an external real-time DO intelligent control system were operated at three different DO concentrations (0.3, 1.0, and 4.0 mgO2/L). Surprisingly, significantly higher values of effluent DON (p<0.05, t-test) and NDMA precursors (p<0.01, t-test) were observed at lower DO levels. Ultrahigh-resolution mass spectrometry analysis showed that molecules produced by microbes at low-DO levels exhibited high proteins/amino sugars-like and low normal oxidation state of carbon characteristics, which possibly acted critical roles in NDMA formation. Furthermore, path analysis by partial least-squares path modeling suggested that NDMA formation potential had strong associations with microbe-DON network stability of microbe-DON co-occurrence interactions (r=0.979, p<0.01). These results highlight the necessity of reconsidering the feasibility of BNR systems operating at low-DO concentrations considering the adverse effects of DON on wastewater discharge and reuse applications.

Motivation of reactive oxidation species in peracetic acid by adding nanoscale zero-valent iron to synergic removal of spiramycin under ultraviolet irradiation: Mechanism and N-nitrosodimethylamine formation potential assessment

In this study, nanoscale zero-valent iron (nZVI) was added to motivate the functions of all the reactive oxidation species in peracetic acid (PAA) mixture under ultraviolet (UV) irradiation, and to enhance the removal of spiramycin, which is a typical precursor of N-nitrosodimethylamine (NDMA). Spiramycin (≤ 10 mg/L) could be completely removed within 20 min under the conditions of an initial pH of 4.0, a nZVI dose of 0.02 g/L and a PAA dose of 3.0 mg/L; additionally, 95.8% and 78.8% of PAA and H2O2 were consumed during the process. Electron paramagnetic resonance analysis and quenching experiments confirmed that 52.4% and 44.8% of spiramycin removal was contributed by hydroxyl radical (•OH) and carbon-centered radicals (R-C•), respectively; and Fe2+ released from nZVI played a critical role in radicals generation. Four degradation pathways of spiramycin were proposed and verified by the density of functional theory analysis. 65.2% of the NDMA formation potential (FP) was reduced after the reaction, and its residual was mainly contributed by the undegraded intermediate of dimethylamine. The results of multiple characterizations and continuous degradation experiments indicated that nZVI was stable in the system as the removal of spiramycin was hardly influenced even if reused three times. The nZVI/UV/PAA process is a promising advanced oxidation technology not only for the removal of refractory NDMA precursors (such as spiramycin) but also for significantly lowering the NDMA FP.

The characteristic of N-nitrosodimethylamine precursor release from algal organic matter and degradation performance of UV/H2O2/O3 technology

Seasonal cyanobacterial blooms in eutrophic water releases algal organic matter (AOM), which contains large amount of dissolved organic nitrogen (DON) and is difficult to be removed effectively by conventional treatment processes (e.g., coagulation and sand filtration) because of its high hydrophilicity. Moreover, N-nitrosodimethylamine (NDMA) can be generated by the reaction of AOM with disinfectants in the subsequent disinfection process. In this study, the formation of NDMA from different AOM components was explored and the control of algal-derived NDMA precursors by UV/H2O2/O3 was evaluated. The results showed that the hydrophilic and polar components of AOM with the low molecular weight had higher NDMA yields. UV-based advanced oxidation process (AOPs) is effective in degrading NDMA precursors, while the removal rate can be affected greatly by UV doses. The removal rate of NDMA precursors by UV/H2O2/O3 is higher than by UV/H2O2 or UV/O3 which can reach 95% at the UV dose of 400 mJ/cm2. An alkaline environment reduces the oxidation efficiency of UV/H2O2/O3 technology, while an acidic environment is conducive to its function. Inorganic anions such as HCO3−, SO42−, Cl− and NO3− are potential to compete with target algal-derived NDMA precursors for the oxidants reaction and inhibit the degradation/removal of these precursors. The degradation of algal-derived NDMA precursors by UV/H2O2/O3 is mainly accomplished by the oxidation of DON with secondary amide groups, and the main degradation mechanism by UV/H2O2/O3 was through the initial decomposition of macromolecular organic compounds such as biopolymers and humic substances and the further degradation of resulting small molecular components.

NDMA and NDMA precursor attenuation in environmental buffers prior to groundwater recharge for potable reuse

Natural attenuation of N-nitrosodimethylamine (NDMA) and NDMA precursors was evaluated in infiltration basins, a riverbed filtration system, and constructed wetlands operated as part of a managed aquifer recharge system. Initial NDMA concentrations up to 9.0 ng/L in infiltration basins (advanced purified, recycled water) before sunrise declined to non-detect (<1.5 ng/L) by 10:00 A.M due to natural photolysis (half-life of 33 to 86 min dependent on solar irradiance). NDMA fortified controls adjacent to the infiltration basin showed similar results, while concentrations in dark controls did not change over the basin's hydraulic retention time. NDMA precursor concentrations did not change significantly in the basin containing advanced-treated water from a potable reuse treatment plant, indicating that photolysis did not remove NDMA precursors nor did photolysis produce a significant amount of precursors. For the other environmental buffers evaluated, NDMA removal was variable through laboratory scale soil columns (22 cm height), in full-scale riverbed filtration system that pre-filters water prior to infiltration basin recharge, and in the constructed wetland. Variability in NDMA removal through the wetlands is attributed to high turbidity. In the case of the riverbed filtration system, variability is likely due to short exposure times to sunlight. For the soil columns, limited NDMA removal is attributed to inefficacy of soil aquifer treatment in removing NDMA over short travel times/distances. NDMA precursors were also ineffectively removed in these systems, with effluent concentrations occasionally exceeding influent concentrations. Overall, the removal of NDMA in environmental buffers utilized for planned or de facto indirect potable reuse is dependent on the system's capacity for photolysis, while NDMA precursors are more recalcitrant and unlikely to be removed in such systems without enhancement or sufficient hydraulic residence times.

Role of ranitidine in N-nitrosodimethylamine formation during chloramination of competing micropollutants

Ranitidine (RNT) is a widely known precursor of N-nitrosodimethylamine (NDMA) as evinced by the self-catalytic formation of NDMA during chloramination. In the present study, the NDMA formation potentials (NDMA-FP) of 26 micropollutants were assessed, particularly when mixed with RNT. 11 compounds were identified as individual precursors, including trimebutine and cimetidine, which exhibited substantial NDMA-FP, with up to 10% molar yield. In addition, nitrosamines, other than NDMA, namely N-nitrosodiethylamine and N-nitrosomethylamine, were observed from diethylamine-containing precursors, such as metoclopramide. In a 1:1 mixture of RNT and a competitor, the change in NDMA-FP was mostly comparable (within 20% deviation), while antagonistic interactions were observed for competitors, such as diethylhydroxylamine. The scattered overall NDMA-FP should be considered as a product of competition among the precursors for core substrates and intermediates for NDMA formation. The co-existence of either trimebutine or metoclopramide with RNT led to an exceptionally synergetic NDMA generation. Degradation kinetics and chlorination/nitrosation experiments combined with mass spectroscopy analyses indicated that RNT would accelerate both the initial chlorination and nitrosation of trimebutine and metoclopramide, leading to N-nitroso complexes, which have well-understood NDMA formation pathways, i.e., amination with subsequent aminyl radical generation. This work demonstrates a wide array of precursors with NDMA-FP, suggesting that nitrosamine formation is potentially underestimated in field environments.

Occurrence of nitrosamines and their precursors in North American drinking waters

AbstractEight N‐nitrosamines were measured at 37 water plants in the United States and Canada. Five tobacco‐specific nitrosamines (TSNAs) were measured in selected waters. N‐Nitrosodimethylamine (NDMA) was preferentially formed in chloraminated systems (maximum detention time: median 4.4 ng/L). A small amount was detected in some chlorinated systems (90th percentile &lt;2.0 ng/L). After ozone (before chloramines), NDMA was sometimes detected (90th percentile 2.9 ng/L), suggesting that the ozone did not react with precursors to form NDMA. The chloramine plants that temporarily switched to chlorine typically produced less NDMA (Plant 29 reduced NDMA formation, on average, from 34 to 4 ng). More NDMA was produced during spring runoff, when there were elevated levels of ammonia and NDMA precursors in the source water. More NDMA was formed when there were higher levels of poly(diallyldimethylammonium chloride) (polyDADMAC) used. N‐Nitrosomorpholene was found to be a contaminant and not a disinfection byproduct; it did not increase during chloramination. TSNAs were produced during spring runoff; source water ammonia impacted the chlor(am)ine chemistry.

Heterogeneous activation of peroxydisulfate by sulfur-doped g-C3N4 under visible-light irradiation: Implications for the degradation of spiramycin and an assessment of N-nitrosodimethylamine formation potential

In this study, peroxydisulfate (PDS) was activated by synthesized sulfur-doped g-C3N4 (SCN) under visible-light irradiation and was adopted to enhance the removal of spiramycin, which is an important precursor of N-nitrosodimethylamine (NDMA). Specifically, 95.4% of spiramycin (≤10 mg/L) was removed in 60 min under the conditions of an initial value of pH of 7.0, an SCN dose of 1.0 g/L, and a PDS dose of 200 mg/L, and its degradation fitted well with the pseudo first-order kinetics. Electron paramagnetic resonance analysis and trapping experiments confirmed that ·O2− and h+ were the main oxidizers for the degradation of spiramycin, and ·SO4− and ·OH also participated in the removal of spiramycin. The removal of spiramycin in the PDS/SCN visible-light catalytic system occurred through three different pathways: aldehyde oxidation, cleavage of C-O bond and demethylation. Notably, 61.4% of NDMA formation potential (FP) was reduced after the reaction. The SCN catalyst was stable and its catalytic performance was excellent in the PDS/SCN system, as the spiramycin removal efficiency decreased only slightly from 95.4% to 87.3% after being reused three times. Therefore, our study not only provides an alternative method for removing spiramycin but can also can significantly reduce NDMA FP.

Fate of N-nitrosodimethylamine and its precursors during a wastewater reuse trial in the Llobregat River (Spain)

In summer 2019, a full-scale trial was carried out to investigate the effects in drinking water quality when tertiary treated wastewater was discharged into the Llobregat River upstream of the intake of one of the major drinking water treatment plants of Barcelona and its metropolitan area. Two scenarios were investigated, i.e. discharging the reclaimed water with and without chemical disinfection with chlorine. This study investigates the concentration of N-nitrosodimethylamine (NDMA) as the specific disinfection conditions employed in this trial may favor its formation. To this aim, both NDMA and NDMA formation potential, were measured. The river contained NDMA at very low concentrations, but the concentration of NDMA precursors was already high. The NDMA concentration was reduced from discharge to the river to drinking water intake probably due to a combined effect of dilution and photolysis. The formation potential was also reduced probably due to dilution and biodegradation. The concentration of NDMA in the drinking water was always low (<7.3 ng/L), although the formation potential was above 10 ng/L in one sample. Dissolved organic matter characterization by high resolution mass spectrometry revealed differences between the nature of the organic matter in the river before and after reclaimed water discharge.

Factors affecting removal of NDMA in an ozone-biofiltration process for water reuse

N-nitrosodimethylamine (NDMA) is a carcinogen and a disinfection byproduct that is formed by ozone and combined chlorine. Various factors affecting NDMA formation and removal were examined at pilot-scale for a treatment train consisting of ozone, biologically-active carbon (BAC) filtration, and granular activated carbon (GAC) adsorption applied to two distinct feed waters. High concentrations of ozone and monochloramine were added to the influent, demonstrating that ozone removed monochloramine precursors of NDMA. Further, longer empty bed contact times (EBCTs) of 10 min for BAC and 10 and 20 min for GAC removed NDMA to <10 ng/L for both feed waters. NDMA removal by the BAC process was most favorable >22 °C, presumably due to elevated microbial activity. A monochloramine residual of 3 mg/L-Cl2 in the BAC influent reduced NDMA removal in the 5 min EBCT BAC from 79% to 36% and in the 10 min EBCT BAC from 88.5% to 73.7%. The absence of ozone in the treatment process significantly reduced NDMA formed post ozone, but decreased NDMA removal in BAC, probably due to lower NDMA concentration in the BAC influent. Finally, adding 5 mg/L of allylthiourea, an inhibitor of ammonia-oxidizing bacteria, indicated that removal mechanisms for ammonia and NDMA are distinct. However, nitrification is still a good indicator for NDMA biodegradation potential, because nitrifying bacteria appear to flourish under similar EBCT, temperature. and monochloramine residual conditions during BAC filtration.

Impact of biological wastewater treatment on the reactivity of N-Nitrosodimethylamine precursors

N-Nitrosodimethylamine (NDMA) is a probable human carcinogen which forms during chloramination of wastewater-impacted drinking waters. Municipal wastewater effluents are considered as major sources of NDMA precursors affecting downstream water quality. To evaluate the deactivation mechanisms and efficiencies of NDMA precursors during secondary treatment with the activated sludge (AS) process, NDMA formation potentials (FPs) of selected model precursor compounds and sewage components (i.e., blackwaters and greywaters) were monitored in batch AS treatment tests. After 24-h incubation with four different types of AS (i.e., domestic rural, domestic urban, textile and lab-grown AS), NDMA FP of trimethylamine (TMA) and minocycline (MNCL) decreased by 77-100%, while there was only 29-46% reduction in NDMA FP of sumatriptan (SMTR). The reduction in NDMA FP associated with ranitidine (RNTD) varied between 34% and 87%. The decrease in NDMA FP of RNTD depended on the AS type, hydraulic retention time (HRT) and solids retention time (SRT). The domestic AS (rural and urban) achieved higher decreases in NDMA FPs of the tested model precursors than the textile AS or lab-grown AS. Increasing the HRT or SRT enhanced NDMA FP decrease for RNTD. Among different processes tested (i.e., biodegradation, biosorption and volatilization), biosorption was the major mechanism responsible for the NDMA FP decrease of RNTD, MNCL and SMTR, while biodegradation was the major NDMA FP reduction mechanism for TMA. The reduction in NDMA FP of RNTD via biodegradation depended on the AS activity which may vary with sampling seasons and SRT. NDMA FPs in all tested sewage components (i.e., blackwaters and greywaters) decreased after 24-h AS treatment. Urine in blackwater was the predominant (i.e., >90%) contributor to NDMA FP in domestic sewage and AS-treated effluents.

Insight into the mechanism of decreasing N-nitrosodimethylamine by Lactobacillus pentosus R3 in a model system

The mechanism of decreasing N-nitrosodimethylamine (NDMA) by Lactobacillus pentosus R3 isolated from Chinese dry sausage was assessed in a model system. The model system was devised using a DeMan-Rogosa and Sharp-ferrous sulfate broth supplement with NDMA or its precursors. The results showed that inoculating L. pentosus R3 could significantly decrease the content of NDMA (P < 0.05). The NDMA precursors (dimethylamine and putrescine) were found to be decreased by L. pentosus R3 (P < 0.05). Nitrite was degraded to nitrosonium cation by acidolysis, which may promote the formation of NDMA. Direct degradation of NDMA by L. pentosus R3 was also observed. The strain exhibited antioxidant activities, including Fe2+ chelating activity, which may be responsible for inhibiting the formation reaction and decreasing the precursors of NDMA. Thus, L. pentosus R3 decreased the content of NDMA possibly by three ways: inhibition of the formation reaction, decrease in precursors (DMA and putrescine) and direct degradation. It is interesting to understand the mechanism of decreasing NDMA by L. pentosus R3 to improve the safety of fermented meat products.

Oxidation of betrixaban to yield N-nitrosodimethylamine by water disinfectants

Degradation of betrixaban, an oral anticoagulant recently approved by the U.S. Food and Drug Administration (FDA), and its N-nitrosodimethylamine (NDMA) formation potential were studied mechanistically in the presence of monochloramine (NH2Cl), free chlorine, and ozone. Upon monochloramination, the formation of NDMA exceeded 1% at basic pH and was significant at circumneutral pH as well. The kinetic studies revealed that the reaction between betrixaban and monochloramine followed pseudo-first-order reaction kinetics. Increasing monochloramine concentration, its reaction time, and pH all significantly enhanced the NDMA formation yield, which also increased three-fold in the presence of bromide during monochloraminantion. The presence of nitrite inhibited the formation of NDMA under the same conditions. This study revealed a new potent and significant precursor of NDMA, indicating that monochloramination of waters containing betrixaban can lead to the formation of NDMA and other disinfection by-products such as dichloroacetonitrile (DCAN) and dimethylformamide (DMF). Moreover, chlorination of betrixaban by hypochlorite also yielded NDMA, albeit at two orders of magnitude lower yield than chloramination, while no NDMA formation was observed from ozonation of betrixaban.

Formation of N-nitrosodimethylamine precursors through the microbiological metabolism of nitrogenous substrates in water

N-nitrosodimethylamine (NDMA) as one emerging disinfection by-product has been investigated globally since 1990s. However, its main precursors are still unclear. We found that NDMA formation potential (NDMAFP) of various water samples increased firstly and then decreased gradually during incubation with microorganism. We hypothesized that NDMA precursors could be produced through metabolism of nitrogenous components and then gradually be biodegraded. To verify this hypothesis, six amino acids (AAs), peptone and ammonium were separately incubated with microorganism and NDMAFP was measured regularly. The average molar yield of the substrates to NDMAFP were 60–200 × 10−6 for the AAs, 350 × 10−6 for peptone under aerobic condition. The extracellular fraction with molecular weight (MW) less than 1 k Dalton contributed the majority to NDMAFP in the peptone experiment, followed by that with MW between 10 k and 0.22 μm and the intracellular materials. Dimethylamine and methylamine were detected during the experiments but their contribution to NDMAFP is quite limited. The results indicate that the nitrosamine precursors may not be the direct metabolite of AAs or peptones but the excretion of living bacteria or the components in dead bacteria body. Our results inferred that AA metabolism may give an NDMAFP of 0.12 nmol/L (maximum) or 0.09 nmol/L (average) in water under aerobic condition. This estimation of NDMAFP from AA metabolism can account for 38% (maximum) or 27% (average) of the median NDMAFP in waters of China (0.32 nmol/L) reported before.