N-nitrosodimethylamine Formation Research Articles

NDMA formation kinetics from three pharmaceuticals in four water matrices

N, N-nitrosodimethylamine (NDMA) is an emerging disinfection by-product (DBP) that has been widely detected in many drinking water systems and commonly associated with the chloramine disinfection process. Some amine-based pharmaceuticals have been demonstrated to form NDMA during chloramination, but studies regarding the reaction kinetics are largely lacking. This study investigates the NDMA formation kinetics from ranitidine, chlorphenamine, and doxylamine under practical chloramine disinfection conditions. The formation profile was monitored in both lab-grade water and real water matrices, and a statistical model is proposed to describe and predict the NDMA formation from selected pharmaceuticals in various water matrices. The results indicate the significant impact of water matrix components and reaction time on the NDMA formation from selected pharmaceuticals, and provide fresh insights on the estimation of ultimate NDMA formation potential from pharmaceutical precursors.

N-nitrosodimethylamine and trihalomethane formation and minimisation in Southeast Queensland drinking water

This study assesses the prevalence of disinfection by-product (DBP) precursors in some Southeast Queensland drinking water sources by conducting formation potential experiments for the four regulated trihalomethanes (THMs), and the potent carcinogen, N-nitrosodimethylamine (NDMA). NDMA formation potentials were consistently low (<5-21 ng/L), and total THM (tTHM) formation potentials were consistently below the Australian Drinking Water Guideline (250 μg/L). NDMA concentration of finished drinking waters was also monitored and found to be <5 ng/L in all cases. The effect of coagulation and advanced oxidation on the formation of NDMA and THMs is also reported. UV/H(2)O(2) pre-treatment was effective in producing water with very low THMs concentrations, and UV irradiation was an effective method for NDMA degradation. H(2)O(2) was not required for the observed NDMA degradation to occur. Coagulation using alum, ferric chloride or poly(diallyldimethylammonium chloride) (polyDADMAC) was ineffective in removing DBPs precursors from the source water studied, irrespective of the low dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) attained. Rather, coagulation with polyDADMAC caused an increase in NDMA formation potential upon chloramination, and all coagulants led to an increased tTHM formation potential upon chlorination due to the high bromide concentration of the source water studied.

Nitrosamine formation from the oxidation of secondary amines

The nitrosamines are potent carcinogens which can be formed as by-products during water treatment. Much recent research activity has been focussed upon the formation, occurrence and control of N-nitrosodimethylamine (NDMA) in particular. In this study, seven secondary amines were oxidised by chlorine, ozone, and UV-irradiation, with and without post-chloramination, to quantify the effect on the formation of seven nitrosamines, including NDMA. While the yields of nitrosamines ranged from 0.01% for N-nitroso-di-n-butylamine (NDBA) to 2.01% for N-nitrosopyrrolidine (NPYR) under conditions of excess monochloramine at pH 7, yields from other oxidants were zero. Pre-oxidation with chlorine reduced nitrosamine formation by up to 83% compared with chloramination alone. This illustrates that in situations where secondary amines are key precursors, chlorine addition before ammonia during chloramination can be expected to limit nitrosamine formation. UV irradiation at 40 mJ cm−2 had little observed impact. Ozonation enhanced NDMA and N-nitrosomethylethylamine (NMEA) formation by subsequent chloramination to 7.48% and 10.15%, respectively.

PolyDADMAC and Dimethylamine as Precursors of N-Nitrosodimethylamine during Ozonation: Reaction Kinetics and Mechanisms

Interactions of ozone with organic precursors during water treatment may generate carcinogenic N-nitrosodimethylamine (NDMA) byproduct. This study investigates the reaction mechanisms responsible for NDMA formation from ozonation of the commonly used poly(diallyldimethylammonium chloride) (polyDADMAC) coagulant. Upon ozonation, polyDADMAC yields the highest amount of NDMA among several water treatment polymers, including polyamines and cationic polyacrylamides. Ozonation transforms polyDADMAC to dimethylamine (DMA) and NDMA formation is correlated to polyDADMAC degradation and DMA release. Hydroxyl radicals generated from ozone play an important role in the degradation of polyDADMAC's quaternary ammonium ring groups and subsequent release of secondary amine. Although nitrite and formaldehyde are detected as ozonation products of DMA and polyDADMAC, contribution of formaldehyde-enhanced nitrosation pathway is determined to be insignificant in NDMA formation. In contrast, reaction of hydroxylamine, another ozonation product of DMA, with DMA in the presence of ozone is deemed critical in the formation of NDMA during ozonation. The study results show that that contact of polyDADMAC with ozone will lead to release of the more potent NDMA precursor DMA but may not generate a significant amount of NDMA under typical drinking water treatment conditions due to low yield. The mechanistic understanding from this study can help develop source control strategies for minimization of NDMA formation risk at water and wastewater utilities.

Occurrence and removal of NDMA and NDMA formation potential in wastewater treatment plants

N-Nitrosodimethylamine (NDMA) is a potent carcinogen that is formed during disinfection by chlorination or ozonation in wastewater treatment plants (WWTPs). At present, little is known about the occurrence and fate of NDMA and its formation potential (FP) during wastewater treatment. We investigated the fate of NDMA and NDMA FP in 12 WWTPs. NDMA occurred in the influents at a concentration ranging from below the limit of quantification (LOQ <10 ng/L) to 80 ng/L, and in the final discharges from below the LOQ to 73 ng/L. In three WWTPs located in industrial areas, the influent had a high NDMA FP (up to 8230 ng/L). The rate of NDMA FP reduction from influent to secondary effluent varied between 85 and 98%, regardless of treatment process. The rate of NDMA removal is due more to the influent properties than to the type of biological treatment process.

Chloramination of nitrogenous contaminants (pharmaceuticals and pesticides): NDMA and halogenated DBPs formation

Disinfection with chloramines is often used to reduce the production of regulated disinfection by-products (DBPs) such as trihalomethanes (THMs) and haloacetic acids (HAAs). However, chloramination can lead to the formation of N-nitrosamines, including N-nitrosodimethylamine (NDMA), a probable human carcinogen. Previous research used dimethylamine (DMA) as a model precursor of NDMA, but certain widely used tertiary dimethylamines (e.g. the pharmaceutical ranitidine) show much higher conversion rates to NDMA than DMA. This study investigates the NDMA formation potential of several tertiary amines including pharmaceuticals and herbicides. The reactivity of these molecules with monochloramine (NH 2Cl) is studied through the formation of NDMA, and other halogenated DBPs such as haloacetonitriles (HANs) and AOX (Adsorbable Organic Halides). Several compounds investigated formed NDMA in greater amounts than DMA, revealing the importance of structural characteristics of tertiary amines for NDMA formation. Among these compounds, the pharmaceutical ranitidine showed the highest molar conversion to NDMA. The pH and dissolved oxygen content of the solution were found to play a major role for the formation of NDMA from ranitidine. NDMA was formed in higher amounts at pH around pH 8 and a lower concentration of dissolved oxygen dramatically decreased NDMA yields. These findings seem to indicate that dichloramine (NHCl 2) is not the major oxidant involved in the formation of NDMA from ranitidine, results in contradiction with the reaction mechanisms proposed in the literature. Dissolved oxygen was also found to influence the formation of other oxygen-containing DBPs (i.e. trichloronitromethane and haloketones). The results of this study identify several anthropogenic precursors of NDMA, indicating that chloramination of waters impacted by these tertiary amines could lead to the formation of significant amounts of NDMA and other non-regulated DBPs of potential health concern (e.g. dichloroacetonitrile or trichloronitromethane). This could be of particular importance for the chloramination of wastewater effluents, especially during water reuse processes.

Occurrence of N-nitrosodimethylamine precursors in wastewater treatment plant effluent and their fate during ultrafiltration-reverse osmosis membrane treatment

The formation of N-nitrosodimethylamine (NDMA) is of major concern among wastewater recycling utilities practicing disinfection with chloramines. The NDMA formation potential (FP) test is a simple and straightforward method to evaluate NDMA precursor concentrations in waters. In this paper we show the NDMA FP results of a range of tertiary wastewater treatment plants that are also the source for production of recycled water using an Ultrafiltration - Reverse Osmosis (UF-RO) membrane process. The results indicate that the NDMA FP of different source waters range from 350 to 1020±20 ng/L. The fate of these NDMA precursors was also studied across the different stages of two Advanced Water Treatment Plants (AWTP) producing recycled water. These results show that more than 98.5±0.5% of NDMA precursors are effectively removed by the Reverse Osmosis (RO) membranes used at the AWTPs. This drastically reduces any potential for re-formation of NDMA after the RO stage even if chloramines may be present (or added) there.

Measurement of dissolved organic nitrogen in a drinking water treatment plant: Size fraction, fate, and relation to water quality parameters

This paper investigates the characteristics of dissolved organic nitrogen (DON) in raw water from the Huangpu River and also in water undergoing treatment in the full-scale Yangshupu drinking water treatment plant (YDWTP) in Shanghai, China. The average DON concentration of the raw water was 0.34 mg/L, which comprised a relatively small portion (~ 5%) of the mass of total dissolved nitrogen (TDN). The molecular weight (MW) distribution of dissolved organic matter (DOM) was divided into five groups: > 30, 10–30, 3–10, 1–3 and < 1 kDa using a series of ultrafiltration membranes. Dissolved organic carbon (DOC), UV absorbance at wavelength of 254 nm (UV254) and DON of each MW fraction were analyzed. DON showed a similar fraction distribution as DOC and UV254. The < 1 kDa fraction dominated the composition of DON, DOC and UV254 as well as the major N-nitrosodimethylamine formation potential (NDMAFP) in the raw water. However, this DON fraction cannot be effectively removed in the treatment line at the YDWTP including pre-ozonation, clarification and sand filtration processes. The results from linear regression analysis showed that DON is moderately correlated to DOC, UV254 and trihalomethane formation potential (FP), and strongly correlated to haloacetic acids FP and NDMAFP. Therefore, DON could serve as a surrogate parameter to evaluate the reactivity of DOM and disinfection by-products FP.

Adsorption of dimethylamine from aqueous solution by manganese dioxide

Removal of precursors of N-nitrosodimethylamine (NDMA), such as the most direct precursor dimethylamine (DMA), might be an effective method to control NDMA formation during practical water treatment process. Adsorption of DMA onto manganese dioxide (MnO₂) from aqueous solution has been investigated using batch experiments in this study. Results indicate that DMA adsorption is initially rapid (in the first 5 h) and the adsorption process reaches a steady state after 15 h. The adsorption isotherms are well described by the Freundlich models. The desorption shows an irreversibility of DMA adsorption onto MnO₂. The effects of temperature, pH, ionic strength, humic acid, and the presence of other secondary aliphatic amines on adsorption processes are also examined. According to the experimental results, the amount of DMA adsorbed increases with an increase of temperature from 288 to 308 K, and with a decrease of ionic strength from 1 to 10 mM. The maximum adsorption appeared at pH 7.0. However, the amount of DMA adsorbed onto MnO₂ does not show obvious difference in the presence of humic acid. According to the results, it suggests that the adsorption is primarily brought about by electrostatic interaction between DMA and MnO₂ surface.

Influence of putrescine, cadaverine, spermidine or spermine on the formation of N-nitrosamine in heated cured pork meat

The influence of biogenic amines (i.e. putrescine, cadaverine, spermidine and spermine) on the N-nitrosamine formation in heated cured lean meat was studied in the presence or absence of sodium nitrite and at different meat processing temperatures. Experimental evidence was produced using gas chromatography with thermal energy analysis detection (GC–TEA). Concentration of N-nitrosamines was modelled as a function of the temperature and the nitrite concentration for two situations, i.e. presence or absence of added biogenic amines to the meat. The significance of the influence of the changing parameters was evaluated by ANOVA (Analysis of Variance).It was found that higher processing temperatures and higher added amounts of sodium nitrite increase the yields of N-nitrosodimethylamine (NDMA) and N-nitrosopiperidine (NPIP). Spermidine and putrescine amplify the formation of NDMA, but spermine and cadeverine do not influence the formation of this N-nitrosamine. Spermidine and cadeverine cause a significant increase of NPIP. Beside N-nitrosopyrrolidine (NPYR) in some rare cases, no other volatile N-nitrosamines are detected.

Understanding the operational parameters affecting NDMA formation at Advanced Water Treatment Plants

N-nitrosodimethylamine (NDMA) can be formed when secondary effluents are disinfected by chloramines. By means of bench scale experiments this paper investigates operational parameters than can help Advanced Water Treatment Plants (AWTPs) to reduce the formation of NDMA during the production of high quality recycled water. The formation of NDMA was monitored during a contact time of 24 h using dimethylamine as NDMA model precursor and secondary effluent from wastewater treatment plants. The three chloramine disinfection strategies tested were pre-formed and in-line formed monochloramine, and pre-formed dichloramine. Although the latter is not employed on purpose in full-scale applications, it has been suggested as the main contributing chemical generating NDMA during chloramination. After 24 h, the NDMA formation decreased in both matrices tested in the order: pre-formed dichloramine > in-line formed monochloramine ≫ pre-formed monochloramine. The most important parameter to consider for the inhibition of NDMA formation was the length of contact time between disinfectant and wastewater. Formation of NDMA was initially inhibited for up to 6 h with concentrations consistently <10 ng/L during these early stages of disinfection, regardless of the disinfection strategy. The reduction of the contact time was implemented in Bundamba AWTP (Queensland, Australia), where NDMA concentrations were reduced by a factor of 20 by optimizing the disinfection strategy.

N-Nitrosodimethylamine Occurrence, Formation and Cycling in Clouds and Fogs

The occurrence, source, and sink processes of N-nitrosodimethylamine (NDMA) have been explored by means of combined laboratory, field, and model studies. Observations have shown the occurrence of NDMA in fogs and clouds at substantial concentrations (7.5-397 ng L(-1)). Laboratory studies were conducted to investigate the formation of NDMA from nitrous acid and dimethylamine in the homogeneous aqueous phase. While NDMA was produced in the aqueous phase, the low yields (<1%) observed could not explain observational concentrations. Therefore gaseous formation of NDMA with partitioning to droplets likely dominates aqueous NDMA formation. Box-model calculations confirmed the predominant contributions from gas phase formation followed by partitioning into the cloud droplets. Measurements and model calculations showed that while NDMA is eventually photolyzed, it might persist in the atmosphere for hours after sunrise and before sunset since the photolysis in the aqueous phase might be much less efficient than in the gas phase.

Demonstration of 20 pharmaceuticals and personal care products (PPCPs) as nitrosamine precursors during chloramine disinfection

The worldwide detection of pharmaceuticals and personal care products (PPCPs) in the aquatic environment and drinking water has been a cause for concern in recent years. The possibility for concurrent formation of nitrosamine DBPs (disinfection by-products) during chloramine disinfection has become another significant concern for delivered drinking water quality because of their potent carcinogenicity. This study demonstrates that a group of PPCPs containing amine groups can serve as nitrosamine precursors during chloramine disinfection. Molar yields higher than 1% are observed for eight pharmaceuticals, with ranitidine showing the strongest potential to form N-nitrosodimethylamine (NDMA). The molar conversion increases with the Cl2:N mass ratio, suggesting that dichloramine is relevant to the formation of NDMA from these precursors. Although the trace level of PPCPs in the environment suggests that they may not account for the majority of nitrosamine precursors during the disinfection process, this study demonstrates a connection between the transformation of PPCPs and the formation of nitrosamines during chloramine disinfection. This both expands the pool of potential nitrosamine precursors, and provides a possible link between the presence of trace levels of certain PPCPs in drinking water sources and potential adverse health effects.

Kinetic assessment and modeling of an ozonation step for full-scale municipal wastewater treatment: Micropollutant oxidation, by-product formation and disinfection

The kinetics of oxidation and disinfection processes during ozonation in a full-scale reactor treating secondary wastewater effluent were investigated for seven ozone doses ranging from 0.21 to 1.24 g O3 g−1 dissolved organic carbon (DOC). Substances reacting fast with ozone, such as diclofenac or carbamazepine (kP,O3 > 104 M−1 s−1), were eliminated within the gas bubble column, except for the lowest ozone dose of 0.21 g O3 g−1 DOC. For this low dose, this could be attributed to short-circuiting within the reactor. Substances with lower ozone reactivity (kP,O3 < 104 M−1 s−1) were only fully eliminated for higher ozone doses.The predictions of micropollutant oxidation based on coupling reactor hydraulics with ozone chemistry and reaction kinetics were up to a factor of 2.5 higher than full-scale measurements. Monte Carlo simulations showed that the observed differences were higher than model uncertainties. The overestimation of micropollutant oxidation was attributed to a protection of micropollutants from ozone attack by the interaction with aquatic colloids. Laboratory-scale batch experiments using wastewater from the same full-scale treatment plant could predict the oxidation of slowly-reacting micropollutants on the full-scale level within a factor of 1.5. The Rct value, the experimentally determined ratio of the concentrations of hydroxyl radicals and ozone, was identified as a major contribution to this difference.An increase in the formation of bromate, a potential human carcinogen, was observed with increasing ozone doses. The final concentration for the highest ozone dose of 1.24 g O3 g−1 DOC was 7.5 μg L−1, which is below the drinking water standard of 10 μg L−1. N-Nitrosodimethylamine (NDMA) formation of up to 15 ng L−1 was observed in the first compartment of the reactor, followed by a slight elimination during sand filtration. Assimilable organic carbon (AOC) increased up to 740 μg AOC L−1, with no clear trend when correlated to the ozone dose, and decreased by up to 50% during post-sand filtration. The disinfection capacity of the ozone reactor was assessed to be 1–4.5 log units in terms of total cell counts (TCC) and 0.5 to 2.5 log units for Escherichia coli (E. coli). Regrowth of up to 2.5 log units during sand filtration was observed for TCC while no regrowth occurred for E. coli. E. coli inactivation could not be accurately predicted by the model approach, most likely due to shielding of E. coli by flocs.

Kinetics and Mechanisms of N-Nitrosodimethylamine Formation upon Ozonation of N,N-Dimethylsulfamide-Containing Waters: Bromide Catalysis

N,N-Dimethylsulfamide (DMS), a newly identified, ubiquitous degradation product of the fungicide tolylfluanide, has been shown to be a N-nitrosodimethylamine (NDMA) precursor during ozonation. In this study, batch ozonation experiments in ultrapure buffered water, surface water, and tap water were performed to determine the kinetics and elucidate the mechanism of NDMA formation from DMS. It was found that at circumneutral pH, DMS reacts slowly with ozone (k approximately 20 M(-1) s(-1)) and moderately with hydroxyl radicals (k=1.5x10(9) M(-1)s(-1)). The reaction of DMS with these oxidants does not lead to NDMA. NDMA was only formed if bromide was present during ozonation of DMS-containing waters. Bromide is oxidized to hypobromous acid (HOBr) by ozone which then reacts with the primary amine of DMS to form a Br-DMS species. The rate limiting step of the formation of Br-DMS is the formation of HOBr. The reaction to form Br-DMS has an apparent second order rate constant at pH 8 of >3x10(4) M(-1)s(-1). The Br-DMS is transformed by ozone to NDMA and nitrate (k>or=5000 M(-1) s(-1)), with yields of 54% and 39%, respectively, based on the primary amine nitrogen of DMS. These reactions release bromide, making bromide a catalyst. NDMA is also formed during ozonation of DMS in the presence of hypochlorous acid (20-30% yield). The last step of NDMA formation is an intramolecular rearrangement with sulfur dioxide extrusion. On the basis of the mechanistic and kinetic information, it was possible to model NDMA formation in DMS-containing Lake Zurich water.

N-nitrosamine formation during chlorination/chloramination of bromide-containing water

This study investigated the impact of bromide on the formation of N-nitrosamines during chlorination and chloramination, and tried to identify the reactive intermediates responsible for variations in the yield of N-nitrosamines. As an intermediate of the reaction between bromide and HOCl, bromine chloride (BrCl) may improve the yield of N-nitrosodimethylamine (NDMA) formation. But increasing the amount of bromide added would result in BrCl being converted into HOBr, which is a weaker oxidant than HOCl. This would result in less nitrite being formed, leading to a decreased yield of NDMA via the nitrosation pathway. When NH4+, was present with the bromide during chlorination, both the rate of formation and yield of N-nitrosamines were improved markedly by highly reactive bromamines. Interestingly, bromide had an inhibitory effect on NDMA formation during the chloramination process when tertiary alkylamines, such as 3-(Dimethylaminomethyl) indole (DMAI) and trimethylamine (TMA), were used as precursors. This phenomenon provides indirect evidence for the hypothesis that the pathway of NDMA formation using tertiary amines with DMA groups is different from that of NDMA formation using secondary alkylamines.

Formation, Detection and Removal of NDMA in Water Treatment Process

N-Nitrosodimethylamine(NDMA) is known as a carcinogenic and mutagenic compound ,and in recent years, it has been found to be a novel disinfection by-product of the chloramination process.The NDMA precursors are considered as dimethylamine(DMA) and tertiary amines with dimethylamine functional groups. There are four pathways to NDMA formation: nitrosation, unsymmetrical dimethylhydrazine(UDMH) oxidation, chlorinated UDMH oxidation and hydroxylamine pathway. Formation of NDMA is affected by the presence of free chlorine and bromide, and pH is also a sensitive fator.The detection and analytical methods of NDMA are usually spectrophotometry，thin-layer chromatography, GC, LC and GC/MS.To improve the detection precision, GC/MS/MS and GC/HRMS are applied in detecting the trace NDMA. The methods of NDMA removal are UV degradation, the resin and several types of zeolite adsorption, UV/ozone and UV/hydrogen peroxide advanced oxidation technologies. Ozone also can oxidate percursors,so it can control the NDMA yield indirectly.

Risk Assessment of N-nitrosodimethylamine Formed Endogenously after Fish-with-Vegetable Meals

The consumption of fish and nitrate-rich vegetables may lead to the formation of the genotoxic carcinogen N-nitrosodimethylamine (NDMA) in the stomach. To assess human cancer risk associated with this formation, a dynamic in vitro gastrointestinal model was used to simulate NDMA formation in the stomach after a fish + vegetable meal. The experimental results were combined with statistical modeling of Dutch food consumption data resulting in predicted exposures to endogenously formed NDMA in the population. The 95th percentile of the long-term exposure distribution was around 4 ng/kg-bw in young children and 0.4 ng/kg-bw in adults. By comparing this exposure with the Benchmark Dose Lower bound (BMDL) 10 for liver cancer in a chronic carcinogenicity study, a chronic margin of exposure (MOE) was calculated of 7000 and 73,000 for young children and adults. Furthermore, the long-term exposure distribution was combined with a dose-response analysis of the liver cancer incidence data to obtain a cancer risk distribution for the human population. The 95th percentile of that distribution was 6 x 10(-6) extra risk for 5-year-old children and 8 x 10(-7) for adults. The liver cancer data allowed for the analysis of the relationship between tumor incidence and time to tumor. For an extra risk of 10(-6), the decrease in time to tumor was conservatively estimated at 3.8 min in the rat, equivalent to 0.1 days in humans. We also combined acute exposure estimates with the BMDL10 from an acute carcinogenicity study for NDMA, resulting in an acute MOE of 110,000. We conclude that the combined consumption of fish and nitrate-rich vegetables appears to lead to marginal increases of additional cancer risk.

Theoretical Investigation of N-Nitrosodimethylamine Formation from Nitrosation of Trimethylamine

Tertiary amines have been demonstrated to be capable of undergoing nitrosative cleavage to produce carcinogenic N-nitrosamines. The reaction mechanism of the nitrosation of trimethylamine (TMA) to produce N-nitrosodimethylamine (NDMA) was investigated at the CBS-QB3 level of theory. The formation of NDMA from TMA was proposed to be initiated by the formation of an iminium ion, Me(2)N(+) horizontal lineCH(2). Two different mechanisms (NOH elimination mechanism and oxidation abstraction mechanism) leading to Me(2)N(+) horizontal lineCH(2) were investigated, and the oxidation abstraction mechanism was found to be mainly operative. This result indicates that the oxidation abstraction mechanism plays an important role in the nitrosation of both N,N-dialkyl aromatic and tertiary aliphatic amines. Starting from the iminium ion, two experimentally proposed mechanisms (pathways 1 and 2) and one new mechanism (pathway 3) were examined. Pathway 1 proposes that the iminium ion undergoes hydrolysis to give dimethylamine (DMA), which then can be further nitrosated to NDMA; pathway 2 proposes that the iminium ion reacts with NO(2)(-) and forms a neutral intermediate, which then collapses to NDMA. In pathway 3, the iminium ion reacts with N(2)O(3) to give NDMA. Calculation results indicate that in aqueous solution pathway 1 is more feasible than pathways 2 and 3; moreover, the transformation from the iminium ion to NDMA is the rate-determining step. This work will be helpful to elucidate the formation mechanisms of the carcinogenic N-nitrosamines from the nitrosation of tertiary amines.

Potential N-nitrosodimethylamine (NDMA) formation from amine-based water treatment polymers in the reactions with chlorine-based oxidants and nitrosifying agents

The NDMA formation potential (NDMA FP) of four commonly used amine-based cationic water treatment polymers was assessed in reactions with chlorine-based oxidants (free chlorine, monochloramine and chlorine dioxide) and nitrosifying agents (nitrite and nitrate). Relatively high dosages of polymers were directly exposed to oxidants for long reaction times in the FP tests to assess the potential to form NDMA and obtain mechanistic insight. Results show that the NDMA FP of the polymers generally follows the trend of aminomethylated polyacrylamide (Mannich polymer)&amp;gt;&amp;gt;poly(epichlorohydrin-dimethylamine) (polyamine) &amp;gt; poly(diallyldimethylammonium chloride) (polyDADMAC) &amp;gt; cationic polyacrylamide copolymer (cationic PAM). The high NDMA FP of Mannich polymer was largely due to the high amount of dimethylamine (DMA) residue in the polymer solution. For the other three polymers, the DMA concentration was increased after oxidation, indicating polymer degradation, and the trend of DMA increase agreed with that of NDMA FP. Among the oxidants, NDMA formation followed the order of monochloramine &amp;gt; free chlorine &amp;gt; chlorine dioxide, despite that the DMA release from the polymers caused by the oxidant followed the opposite order. At equal dosages, nitrite and nitrate generated NDMA from the polymers at levels comparable to those by free chlorine and chlorine dioxide; even so, the nitrosifying agents are unlikely to contribute significantly to NDMA formation due to expected lower concentrations in drinking water treatment systems. Jar tests followed by monochloramination of real water samples using conditions in line with those at potable water treatment plants generally showed relatively small contributions from polyamines and polyDADMACs to the overall NDMA formation.