Concentrations Of N-nitrosodimethylamine Precursors Research Articles

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).

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.

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.

Monitoring NDMA precursors throughout membrane-based advanced wastewater treatment processes by organic matter fluorescence

This study investigates the potential of fluorescence excitation/emission matrices (EEM) measurement as a tool to predict N-Nitrosodimethylamine (NDMA) formation in water reuse applications. In particular, samples from a pilot-scale membrane biological reactor (MBR) followed by nanofiltration (NF) advanced water treatment plant, are used for the study. Concentrations of both, specific NDMA precursors and NDMA formation potential (FP) are correlated with different EEM peaks. The specific precursors investigated are: erythromycin, azithromycin, clarithromycin, venlafaxine, o-desmethylvenlafaxine, ranitidine and citalopram, while the NDMA FP is conventionally measured by the NDMA formation potential test. EEM peaks investigated are obtained by fluorescence regional integration as well as by the peak picking method generating I1, I2, I3, I4, and I5 peaks. Results showed that protein-like materials are correlated with the bulk NDMA FP and specific NDMA precursors. Additionally, selected fluorescence peaks such as I1, I2 and I4 are strongly correlated with NDMA precursors throughout the MBR-NF pilot plant. The removal of NDMA precursors and EEM peaks also correlated well (R2 > 0.8). This data shows that fluorescence EEM can be a promising tool to monitor the concentration of NDMA precursors and their removal in water reuse application.

Bench-scale column evaluation of factors associated with changes in N-nitrosodimethylamine (NDMA) precursor concentrations during drinking water biofiltration

Biofiltration has been observed to increase or decrease the concentrations of N-nitrosodimethylamine (NDMA) precursors in the effluents of full-scale drinking water facilities, but these changes have been inconsistent over time. Bench-scale tests comparing biofiltration columns side-by-side exposed to different conditions were employed to characterize factors associated with changes in NDMA precursor concentrations, as measured by application of chloramines under uniform formation conditions (UFC). Side-by-side comparisons of biofiltration media from different facilities fed with water from each of these facilities demonstrated that differences in source water quality were far more important than any original differences in the microbial communities on the biofiltration media for determining whether NDMA precursor concentrations increased, decreased or remained constant across biofilters. Additional tests involving spiking of specific constituents hypothesized to promote increases in NDMA precursor concentrations demonstrated that inorganic nitrogen species associated with nitrification, including ammonia, hydroxylamine and chloramines, and biotransformation of known precursors (i.e., municipal wastewater and the cationic polymer, polyDADMAC) to more potent forms were not important. Biotransformation of uncharacterized components of source waters determined whether NDMA precursor concentrations increased or decreased across biofilters. These uncharacterized source water component concentrations varied temporally and across locations. Where biotransformation of source water precursors increased NDMA precursor concentrations, ∼30–60% of the levels observed in column effluents fed with biofiltration influent water remained associated with the media and could be rinsed therefrom in either the dissolved or particulate form. Ozone pre-treatment significantly reduced NDMA precursor concentrations at one facility, suggesting that pre-oxidation could be an effective technique to mitigate the increase in NDMA precursor concentrations during biofiltration. Biofiltration decreased the concentrations of halogenated disinfection byproduct precursors.

N-nitrosodimethylamine (NDMA) formation at an indirect potable reuse facility

Full-scale experiments to evaluate N-nitrosodimethylamine (NDMA) formation and attenuation were performed within an advanced indirect potable reuse (IPR) treatment system, which includes, sequentially: chloramination for membrane fouling control, microfiltration (MF), reverse osmosis (RO), ultraviolet irradiation with hydrogen peroxide (UV/H2O2), final chloramination, and pH stabilization. Results of the study demonstrate that while RO does effectively remove the vast majority of NDMA precursors, RO permeate can still contain significant concentrations of NDMA precursors resulting in additional NDMA formation during chloramination. Thus, it is possible for this advanced treatment system to produce water with NDMA levels higher than regional requirements for potable applications (10 ng/L). The presence of H2O2 during UV oxidation reduced NDMA photolysis efficiency and increased NDMA formation (∼22 ng/L) during the secondary chloramination and lime stabilization. This is likely due to formation of UV/H2O2 degradation by-products with higher NDMA formation rate than the parent compounds. However, this effect was diminished with higher UV doses. Bench-scale experiments confirmed an enhanced NDMA formation during chloramination after UV/H2O2 treatment of dimethylformamide, a compound detected in RO permeate and used as model precursor in this study. The effect of pre-ozonation for membrane fouling control on NDMA formation was also evaluated at pilot- (ozone-MF-RO) and bench-scale. Relatively large NDMA formation (117–227 ng/L) occurred through ozone application that was dose dependent, whereas chloramination under typical dosages and contact times of IPR systems resulted in only a relatively small increase of NDMA (∼20 ng/L). Thus, this research shows that NDMA formation within a potable water reuse facility can be challenging and must be carefully evaluated and controlled.

A Practical LC-MS/MS Method for the Detection of NDMA at Nanogram per Liter Concentrations in Multiple Water Matrices

N-nitrosodimethylamine (NDMA) is one of the most important disinfection by-products (DBPs) due to its carcinogenicity even at low concentrations which correspond to the levels occurring in drinking water and wastewater effluents. Therefore, NDMA is a candidate DBP that is expected to be regulated in the near future. However, the measurement of NDMA in the low nanogram per liter range is challenging because of the limitations of analytical techniques including both the sample preparation and the LC-MS/MS. Moreover, the accuracy of most of the current methods is only tested for drinking water and no information is present for other matrices. In this study, a combination of solid-phase extraction (SPE) and LC-MS/MS method that does not require high-resolution MS or advanced techniques for sample pretreatment is developed. Moreover, important factors that affect the optimization of the SPE method are provided to enable readers to optimize their own SPE procedures if necessary. The proposed method was validated for surface water, groundwater, and wastewater samples and the method quantification limit was 2 ng/L. In addition, the proposed method was used to determine the concentration of NDMA precursors measured as NDMA formation potential (NDMAFP) throughout a drinking water treatment plant at two different sampling periods. NDMAFP decreased by approximately 40 % in both samples. The concentrations ranged between 4 and 11.5 ng/L and the presence of these low concentrations underlines the need for an easy to use, yet sensitive method for the determination of NDMA in environmental matrices.

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.

The fate of wastewater-derived NDMA precursors in the aquatic environment

To assess the stability of precursors of the chloramine disinfection byproduct N-nitrosodimethylamine (NDMA) under conditions expected in effluent-dominated surface waters, effluent samples from four municipal wastewater treatment plants were subjected to chlorination and chloramination followed by incubation in the presence of inocula derived from activated sludge. Samples subjected to free chlorine disinfection showed lower initial concentrations of NDMA precursors than those that were not chlorinated or were disinfected with pre-formed chloramines. For chloraminated and control (unchlorinated) treatments, the concentration of NDMA precursors decreased by an average of 24% over the 30-day incubation in samples from three of the four facilities. At the fourth facility, where samples were collected on three different days, NDMA precursor concentrations decreased by approximately 80% in one sample and decreased by less than 20% in the other two samples. In contrast to the low reactivity of the NDMA precursors, NDMA disappeared within 30 days under the conditions employed in these experiments. These results and measurements made in an effluent-dominated river suggest that although NDMA may be removed after wastewater effluent is discharged, wastewater-derived NDMA precursors could persist long enough to form significant concentrations of NDMA in drinking water treatment plants that use water originating from sources that are subjected to wastewater effluent discharges.

Precursors of N-Nitrosodimethylamine in Natural Waters

Monochloramine disinfection of drinking water can result in the formation of the potent carcinogen N-nitrosodimethylamine (NDMA). To assess NDMA precursor concentrations in natural waters, samples from lakes, reservoirs, groundwaters, and isolated natural organic matter were exposed to relatively high concentrations of monochloramine. After 1 week, the concentration of NDMA ranged from approximately 0.1 to 0.8 nM. Application of a sensitive new GC/MS/MS technique and amendment of a sample with the known NDMA precursor dimethylamine (DMA) prior to chloramination indicated that only a small fraction of the NDMA produced during chloramination could be attributable to DMA. Chloramination of isolated natural organic matter and application of solid-phase extraction prior to chloramination suggested that natural organic matter accounts for a significant fraction of the precursors. However, the concentrations of NDMA precursors were higher in the epilimnion than the hypolimnion of two stratified reservoirs despite similar concentrations of dissolved organic carbon throughout the water column. Experiments performed to simulate the formation of NDMA during conditions comparable to those encountered in water treatment and distribution systems that use chloramine indicated that the concentration of NDMA produced from naturally occurring precursors usually will be less than 0.1 nM. The results indicate that chloramination of natural organic matter alone is unlikely to produce NDMA levels exceeding the current regulations.