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Biofiltration has been shown to be effective for disinfection by-product (DBP) precursor control, however few studies have considered its role in the potential formation of DBPs. Biofilm is composed of heterogeneous bacteria as well as extracellular polymeric substances (EPS). The objective of this study was to determine the contribution of biofilm-related materials such as EPS to form nitrogen-containing DBPs upon chloramination, and to determine the influence of cyclical (scheduled on-off) biofilter operation on DBP precursor removal. Biologically active media was sampled from a full-scale biofilter operating under cold-water conditions (3.6 ± 0.5 °C) and extracted using a cation exchange resin into a phosphate buffer solution. Biomass concentrations, as determined using adenosine triphosphate (ATP) measurements, remained stable at 298 ± 55 ng ATP/g media over the trial period. N-nitrosodimethylamine (NDMA) and haloacetonitrile (HAN 4) formation potential (FP) tests conducted under uniform formation conditions (UFC) using extracted biofilm yielded 0.80 ± 0.27 ng NDMA/g media and 18.7 ± 3.3 ng dichloroacetonitrile (DCAN)/g media. Further analyses of extracted biofilm using fluorescence spectroscopy and liquid chromatography-organic carbon detection indicated the presence of proteins above 20 kDa and humic-like substances. Extracted proteins (93.5 ± 8.1 μg/g media) correlated well (R = 0.90) with UV 280 measurements, indicating that spectrophotometry may serve as a valuable tool to quantify proteins in extracted biofilms. While substances in biofilms can serve as NDMA and DCAN precursors, the full-scale cyclically-operated biofilter that was examined did not show release of NDMA precursors during start-up following stagnation periods of 6 h or more. These biofilters consistently removed 6.9 ± 4.3 ng/L of NDMA precursors; typical NDMA UFC-FP of biofilter effluent was 8.5 ± 2.6 ng/L. Graphical abstract Image 1 Highlights • Biofilm extracted from filter media contained 93.5 ± 8.1 μg proteins/g media. • Extracted biofilm produced 0.80 ± 0.27 ng NDMA and 18.7 ± 3.3 ng DCAN per g media. • Biofiltration removed ∼50% of NDMA precursors during typical steady-state operation. [ABSTRACT FROM AUTHOR]

Abstract N-nitrosodimethylamine (NDMA) is a chloramine disinfection by-product, and its formation in drinking waters can increase due to the addition of cationic polydiallyldimethylammonium chloride (polyDADMAC). PolyDADMAC is a cationic polymer added as a coagulant or coagulant aid to enhance turbidity removal during sedimentation and filtration. This paper answers two central questions to understanding the nature of the NDMA precursors in polyDADMAC. First, what is the reactivity of different molecular weight (MW) fractions of polyDADMAC with chloramines? NDMA formation potential (NDMAFP) and kinetic experiments with chloramines were conducted for non-fractionated (raw) and size-excluded fractions (<3K, 3–10K, and >10K Da.) of polyDADMAC. The lower MW fraction (<3K Da.) of polyDADMAC solutions was responsible for forming 64 ± 6% of the NDMA, despite containing only 8.7 and 9.8% of the carbon or nitrogen present in the bulk polymer. The chloramine demand kinetics of the lowest MW fraction were also >2× faster than the higher MW fractions. Therefore, in a water treatment application the lower MW polyDADMAC likely contributes to most of the NDMA attributed to the use of polyDADMAC. The second question was: can 1H and 13C nuclear magnetic resonance spectroscopy (NMR) be used to characterize the molecular structures in polyDADMAC that react with chloramines? A peak for 1H NMR dimethylamine (DMA), a known low MW NDMA precursor, was found in a commercial polyDADMAC solution and decreased upon chloramination. The estimated DMA alone could not account for the observed NDMAFP, indicating the presence of other low MW precursors. Diffusion order spectroscopy (DOSY) NMR also showed multiple lower MW organics in polyDADMAC that change upon chloramination, including a 1.5× decrease in MW, suggesting chloramines cleave C C or C N bonds. These reactions may produce intermediates responsible for NDMA formation. Polymer manufacturers could use NMR to synthesize polyDADMAC with less DMA and other low MW compounds that produce NDMA upon chloramination. Graphical abstract Image 1 Highlights • The reactivity of low MW fraction of polyDADMAC (<3K Da.) was highest compared with bulk and fractionated polyDADMAC. • A second order model of NDMA formation is proposed to describe NDMA formation kinetics by polyDADMAC upon chloramination. • Carbon and proton NMR experiments were performed to characterize the polyDADMAC molecular structures after chloramination. [ABSTRACT FROM AUTHOR]

Direct potable reuse is becoming a feasible option to cope with water shortages. It requires more stringent water quality assurance than indirect potable reuse. Thus, the development of a high-rejection reverse osmosis (RO) membrane for the removal of one of the most challenging chemicals in potable reuse – N -nitrosodimethylamine (NDMA) – ensures further system confidence in reclaimed water quality. This study aimed to achieve over 90% removal of NDMA by modifying three commercial and one prototype RO membrane using heat treatment. Application of heat treatment to a prototype membrane resulted in a record high removal of 92% (1.1-log) of NDMA. Heat treatment reduced conductivity rejection and permeability, while secondary amines, selected as N -nitrosamine precursors, were still well rejected (>98%) regardless of RO membrane type. This study also demonstrated the highly stable separation performance of the heat-treated prototype membrane under conditions of varying feed temperature and permeate flux. Fouling propensity of the prototype membrane was lower than a commercial RO membrane. This study identified a need to develop highly selective RO membranes with high permeability to ensure the feasibility of using these membranes at full scale. [ABSTRACT FROM AUTHOR]

The ex situ treatment of N-nitrosodimethylamine (NDMA) and N-nitrodimethylamine (NTDMA) in groundwater was evaluated in a field-scale fluidized bed bioreactor (FBR). Both of these compounds, which originally entered groundwater at the test site from the use of liquid rocket propellant, are suspected human carcinogens. The objective of this research was to examine the application of a novel field-scale propane-fed fluidized bed bioreactor as an alternative to ultraviolet irradiation (UV) for treating NDMA and NTDMA to low part-per-trillion (ng/L) concentrations. Previous laboratory studies have shown that the bacterium Rhodococcus ruber ENV425 can biodegrade NDMA and NTDMA during growth on propane as a primary substrate and that the strain can effectively reduce NDMA concentrations in propane-fed bench-scale bioreactors of different design. R. ruber ENV425 was used as a seed culture for the FBR, which operated at a fluidization flow of ∼19 L-per-min (LPM) and received propane, oxygen, and inorganic nutrients in the feed. The reactor effectively treated ∼1 μg/L of influent NDMA to effluent concentrations of less than 10 ng/L at a hydraulic residence time (HRT) of only 10 min. At a 20 min HRT, the FBR reduced NDMA to <4.2 ng/L in the effluent, which was the discharge limit at the test site where the study was conducted. Similarly, NTDMA was consistently treated in the FBR from ∼0.5 μg/L to <10 ng/L at an HRT of 10 min or longer. Based on these removal rates, the average NDMA and NTDMA elimination capacities achieved were 2.1 mg NDMA treated/m 3 of expanded bed/hr of operation and 1.1 mg NTDMA treated/m 3 of expanded bed/hr of operation, respectively. The FBR system was highly resilient to upsets including power outages. Treatment of NDMA, but not NTDMA, was marginally affected when trace co-contaminants including trichloroethene (TCE) and trichlorofluoromethane (Freon 11) were initially added to feed groundwater, but performance recovered over a few weeks in the continued presence of these compounds. Strain ENV425 appeared to be replaced by native propanotrophs over time based on qPCR analysis, but contaminant treatment was not diminished. The results suggest that a FBR can be a viable alternative to UV treatment for removing NDMA from groundwater. [ABSTRACT FROM AUTHOR]

Water treatment combining advanced oxidative processes with subsequent exposure to biological activated carbon (BAC) holds promise for the attenuation of recalcitrant pollutants. Here we contrast oxidation and subsequent biofiltration of treated wastewater effluent employing either ozone or UV/H 2 O 2 followed by BAC during pilot-scale implementation. Both treatment trains largely met target water quality goals by facilitating the removal of a suite of trace organics and bulk water parameters. N -nitrosodimethylamine (NDMA) formation was observed in ozone fed BAC columns during biofiltration and to a lesser extent in UV/H 2 O 2 fed columns and was most pronounced at 20 min of empty bed contact time (EBCT) when compared to shorter EBCTs evaluated. While microbial populations were highly similar in the upper reaches, deeper samples revealed a divergence within and between BAC filtration systems where EBCT was identified to be a significant environmental predictor for shifts in microbial populations. The abundance of Nitrospira in the top samples of both columns provides an explanation for the oxidation of nitrite and corresponding increases in nitrate concentrations during BAC transit and support interplay between nitrogen cycling with nitrosamine formation. The results of this study demonstrate that pretreatments using ozone versus UV/H 2 O 2 impart modest differences to the overall BAC microbial population structural and functional attributes, and further highlight the need to evaluate NDMA formation prior to full-scale implementation of BAC in potable reuse applications. [ABSTRACT FROM AUTHOR]

Water quality remains one of the greatest concerns with regards to human health. Advances in science and technology have resulted in highly efficient water treatment plants, significantly reducing diseases related to waterborne pathogenic microorganisms. While disinfection is critical to mitigate pathogen risk to humans, the reactions between the disinfectant and dissolved organic compounds can lead to the formation of chemical contaminants called disinfection by-products (DBPs). DBPs have been related to numerous health issues including birth defects and cancer. The formation of disinfection by-products occurs due to the reaction of oxidants and natural organic matter. DBP precursors are derived from anthropogenic sources including pharmaceuticals and chemical waste, the breakdown of vegetation from external catchment sources (allochthonous) and internally derived sources including phytoplankton (autochthonous). Current literature focuses on the contribution of allochthonous sources towards the formation of DBPs, however, the recalcitrant nature of hydrophilic phytoplankton derived organic matter indicates that autochthonous derived organic carbon can significantly contribute to total DBP concentrations. The contribution of phytoplankton to the formation of DBPs is also influenced by cellular exudation rates, chemical composition, environmental conditions and the physical and chemical conditions of the solution upon disinfection. Formation of DBPs is further influenced by the presence of cyanobacteria phyla due to their notoriety for forming dense blooms. Management of DBP formation can potentially be improved by reducing cyanobacteria as well as DBP precursors derived from other phytoplankton. [ABSTRACT FROM AUTHOR]

The formation of the carcinogen N-nitrosodimethylamine (NDMA) during drinking water treatment has raised concerns in the drinking water industry. Many bench-scale laboratory tests and pilot plant studies have been completed to try to determine which factors during water treatment increase or decrease the amount of NDMA formed in drinking water. This study used data from over 20 drinking water treatment plants in the United States and Canada to determine which factors are most highly correlated with the NDMA concentration in delivered water using a mixed effects model with a random intercept. This type of analysis has not been used previously with trihalomethane (THM) models due to the fact that those studies did not sample such a large number and range of plants as was done in this NDMA study. Ultraviolet absorbance at 254 nm (UV254) in the plant influent and pre-chlorination time used at the plant were highly correlated in all models with NDMA concentration in finished water as well as the percentage change between NDMA formation potential in the plant influent and actual formation in the finished water. Specifically, an increase in UV254 absorbance in a model was associated with an increase in NDMA and an increase in pre-chlorination time in a model was associated with a decrease in NDMA. Other water quality parameters including sucralose concentration in the plant influent, polyDADMAC polymer dose, pH, and chlorine-to-ammonia weight ratio used in the plant were also correlated with NDMA concentration in the distribution system. Lastly, NDMA precursor loading was correlated with the use of polyDADMAC (where precursors were added) and the use of ozone and granular activated carbon (GAC) treatment (where precursors were removed). [ABSTRACT FROM AUTHOR]

Removal of N -nitrosodimethylamine (NDMA) in drinking water treatment poses a significant technical challenge due to its small molecular size, high polarity and water solubility, and poor biodegradability. Degradation of NDMA and its precursor, dimethylamine (DMA), was investigated by adsorbing them from aqueous solution using porous mineral sorbents, followed by destruction under microwave irradiation. Among the mineral sorbents evaluated, dealuminated ZSM-5 exhibited the highest sorption capacities for NDMA and DMA, which decreased with the density of surface cations present in the micropores. In contrast, the degradation rate of the sorbed NDMA increased with the density of surface cations under microwave irradiation. Evolutions of the degradation products and C/N ratio indicate that the sorbed NDMA and DMA could be eventually mineralized under continuous microwave irradiation. The degradation rate was strongly correlated with the bulk temperature of ZSM-5 and microwave power, which is consistent with the mechanism of pyrolysis caused by formation of micro-scale “hot spots” within the mineral micropores under microwave irradiation. Compared to existing treatment options for NDMA removal, microporous mineral sorption coupled with microwave-induced degradation has the unique advantages of being able to simultaneously remove NDMA and DMA and cause their full mineralization, and thus could serve as a promising alternative method. [ABSTRACT FROM AUTHOR]

N -Nitrosodimethylamine (NDMA) is a disinfection by-product (DBP) that is potentially carcinogenic and has been found to occur in drinking water treatment systems impacted with treated wastewater. A major gap in NDMA research is an understanding of the persistence of wastewater-derived precursors within the natural environment. This research sought to fill this knowledge gap by surveying NDMA precursors across the length of a wastewater effluent-dominated wash. Significant precursor reduction (17%) was found to occur from introduction into the wash to a point 9 h downstream. This reduction translates into a half-life of roughly 32 h for bulk NDMA precursors. Further laboratory experiments examining rates of photolysis, biodegradation and loss to sediments, illustrated that both photolytic and biological degradation were effective removal mechanisms for NDMA precursors. Loss to sediments that were acquired from the wash did not appear to reduce NDMA precursors in the water column, although a control conducted with DI water provided evidence that significant NDMA precursors could be released from autoclaved sediments (suggesting that sorption does occur). Microbial experiments revealed that microbes associated with sediments were much more effective at degrading precursors than microbes within the water column. Overall, this study demonstrated that natural processes are capable of attenuating NDMA precursors relatively quickly within the environment, and that utilities might benefit from maximizing source water residency time in the environment, prior to introduction into treatment plants. [ABSTRACT FROM AUTHOR]

Wastewater reuse is currently considered globally as the most critical element of sustainable water management. The dissolved effluent organic matter (dE f OM) present in biologically treated urban wastewater, consists of a heterogeneous mixture of refractory organic compounds with diverse structures and varying origin, including dissolved natural organic matter, soluble microbial products, endocrine disrupting compounds, pharmaceuticals and personal care products residues, disinfection by-products, metabolites/transformation products and others, which can reach the aquatic environment through discharge and reuse applications. dE f OM constitutes the major fraction of the effluent organic matter (E f OM) and due to its chemical complexity, it is necessary to utilize a battery of complementary techniques to adequately describe its structural and functional character. dE f OM has been shown to exhibit contrasting effects towards various aquatic organisms. It decreases metal uptake, thus potentially reducing their bioavailability to exposed organisms. On the other hand, dE f OM can be adsorbed on cell membranes inducing toxic effects. This review paper evaluates the performance of various advanced treatment processes (i.e., membrane filtration and separation processes, activated carbon adsorption, ion-exchange resin process, and advanced chemical oxidation processes) in removing dE f OM from wastewater effluents. In general, the literature findings reveal that dE f OM removal by advanced treatment processes depends on the type and the amount of organic compounds present in the aqueous matrix, as well as the operational parameters and the removal mechanisms taking place during the application of each treatment technology. [ABSTRACT FROM AUTHOR]

Abstract: N-nitrosodimethylamine (NDMA), as a new disinfection byproduct, is a potential carcinogen. In this study, we focused on the role of ozone in NDMA degradation. We characterized the removal efficiency, influencing factors and degradation mechanism. Our results demonstrated that ozonation was an efficient process for NDMA degradation. The removal efficiency was affected by initial NDMA concentration; higher NDMA dosing required higher ozone utilization. NDMA oxidation was favored at high ozone dosage and high pH. NDMA ozonation under various pH as well as hydroxyl radical ( OH) inhibition experiments verified that OH generated from ozone dominated NDMA oxidation. The main products of NDMA ozonation were methylamine (MA), dimethylamine (DMA), nitromethane (NM) and ammonium (AM). Their yields changed with the amount of ozone provided. A NDMA ozonation mechanism was proposed. It is suggested that NDMA degradation is induced by OH attacking through any of four pathways, with oxygen involving in the oxidation process. MA generation was due to OH attacking on amine nitrogen and methyl group. DMA formation was related to OH attacking on nitrosyl nitrogen via a parallel pathway. We speculate that supersaturated dissolved oxygen by ozone decomposition is responsible for NM generation by further oxidation of MA and DMA. AM formation may be favored due to MA degradation under OH exposure. [Copyright &y& Elsevier]

Abstract: The direct incorporation of chloramines and dissolved organic nitrogen (DON) may provide the nitrogen for nitrogenous disinfection byproducts (N-DBPs). This study explores the contributions of natural DON and chloramine incorporation to the formation of N-DBPs during chloramination. This study also evaluates the relationship between N-DBPs and carbonaceous DBPs by investigating four sources of dissolved organic matter with different DON-to-dissolved organic carbon (DOC) ratios. During chloramination, dihaloacetonitrile (DXAN) formation is correlated with the summation of trihalomethanes (THMs) and dichloroacetic acids (DXAAs) yield in molar basis at pH > 6. This study tests the formation kinetics of THMs, DXAAs, and DXANs during chloramination, explores the changes in DBP formation potential before and after a sequence of ozonation and chloramination, and tracks the nitrogen source of dichloroacetonitrile. The results support the hypothesis that THMs, DXAAs, and DXANs mainly derive from similar precursors upon chloramination. In addition, the precursor of HANs was approximately 10% (on a molar basis) of that of THMs and HAAs combined. The N-nitrosodimethylamine (NDMA) formation potential is correlated with DON/DOC in hydrophilic and transphilic fractions. Isotope 15N-labeled monochloramine coupled with LC-electrospray ionization-tandem mass spectrometry was used to explore the nitrogen source of NDMA formed in chloraminated organic fractions. The results indicate that the nitroso group of the formed NDMA originates mainly from chloramines. [Copyright &y& Elsevier]

Abstract: N-nitrosodimethylamine (NDMA) is a suspected human carcinogen that has traditionally been treated in water using ultraviolet irradiation (UV). The objective of this research was to examine the application of a laboratory-scale fluidized bed reactor (FBR) as an alternative technology for treating NDMA to part-per-trillion (ng/L) concentrations in groundwater. Previous studies have shown that the bacterium Rhodococcus ruber ENV425 is capable of cometabolizing NDMA during growth on propane as a primary substrate in batch culture (Fournier et al., 2009) and in a bench-scale membrane bioreactor (Hatzinger et al., 2011) to low ng/L concentrations. R. ruber ENV425 was inoculated into the FBR during this study. With a hydraulic residence time (HRT) of 20 min, the FBR was found to be an effective means to treat 10–20 μg/L of NDMA to effluent concentrations less than 100 ng/L. When the HRT was increased to 30 min and oxygen and propane addition rates were optimized, the FBR system demonstrated treatment of the NDMA to effluent concentrations of less than 10 ng/L. Short-term shutdowns and the presence of trichloroethene (TCE) at 6 μg/L as a co-contaminant had minimal effect on the treatment of NDMA in the FBR. The data suggest that the FBR technology can be a viable alternative to UV for removing NDMA from groundwater. [Copyright &y& Elsevier]

Abstract: N-nitrosodimethylamine (NDMA) is an emerging disinfection by-product (DBP) which can be formed via the chloramination of amine-based precursors. The formation of NDMA is mainly determined by the speciation of chloramines and the precursor amine groups, both of which are highly dependent on pH. The impact of pH on NDMA formation has been studied for the model precursor dimethylamine (DMA) and natural organic matter (NOM), but little is known for amine-based pharmaceuticals which have been newly identified as a group of potential NDMA precursors, especially in waters impacted by treated wastewater effluents. This study investigates the role of pH in the formation of NDMA from two amine-based pharmaceuticals, ranitidine and sumatriptan, under drinking water relevant conditions. The results indicate that pH affects both the ultimate NDMA formation as well as the reaction kinetics. The maximum NDMA formation typically occurs in the pH range of 7–8. At lower pH, the reaction is limited due to the lack of non-protonated amines. At higher pH, although the initial reaction is enhanced by the increasing amount of non-protonated amines, the ultimate NDMA formation is limited because of the lack of dichloramine. [Copyright &y& Elsevier]

Abstract: Two most commonly used dithiocarbamate (DTC) pesticides, dimethyldithiocarbamate (DMDTC) and diethyldithiocarbamate (DEDTC), were examined in this study to evaluate their potential to form nitrosamines when in contact with various water disinfection oxidants. Results show that DTCs can serve as nitrosamine precursors, by release of secondary amines through hydrolysis or through reactions with oxidants. The reactions of DTCs with monochloramine and ozone were found to be particularly problematic in the risk of generating nitrosamines, though all four tested oxidants, including free chlorine and chlorine dioxide, formed nitrosamines. NDEA yield from DEDTC was lower, by different degrees, than NDMA yield from DMDTC for all four oxidants, which was attributed to the steric hindrance associated with bulkier reaction intermediate that are more difficult to be further oxidized to form nitrosamine. The yield of nitrosamines increased with the oxidant dosage for both monochloramination and ozonation of DTCs. Results for nitrosamine formation from DTCs at varying pH were found to be consistent with the pH trend of nitrosamine formation from ozonation and monochloramination of secondary amines. Kinetic study results and identification and quantification of reaction products suggest that the DTCs were not significant direct precursors of nitrosamines during monochloramination or ozonation, but rather nitrosamines formed were primarily from reaction of oxidants with the amine which may be generated either through hydrolysis or through oxidation of DTCs. [Copyright &y& Elsevier]

Abstract: N-Nitrosamines are a class of disinfection by-products (DBPs) that have been reported to be more toxic than the most commonly detected and regulated DBPs. Only a few studies investigating the formation of N-nitrosamines from disinfection of natural waters have been reported, and little is known about the role of natural organic matter (NOM) and the effects of its nature and reactivity on the formation of N-nitrosamines. This study investigated the influence of the molecular weight (MW) characteristics of NOM on the formation of eight species of N-nitrosamines from chlorination and chloramination, and is the first to report on the formation of eight N-nitrosamines from chlorination and chloramination of MW fractions of NOM. Isolated NOM from three different source waters in Western Australia was fractionated into several apparent MW (AMW) fractions using preparative-scale high performance size exclusion chromatography. These AMW fractions of NOM were then treated with chlorine or chloramine, and analysed for eight species of N-nitrosamines. Among these N-nitrosamines, N-nitrosodimethylamine (NDMA) was the most frequently detected. All AMW fractions of NOM produced N-nitrosamines upon chlorination and chloramination. Regardless of AMW characteristics, chloramination demonstrated a higher potential to form N-nitrosamines than chlorination, and a higher frequency of detection of the N-nitrosamines species was also observed in chloramination. The results showed that inorganic nitrogen may play an important role in the formation of N-nitrosamines, while organic nitrogen is not necessarily a good indicator for their formation. Since chlorination has less potential to form N-nitrosamines, chloramination in pre-chlorination mode was recommended to minimise the formation of N-nitrosamines. There was no clear trend in the formation of N-nitrosamines from chlorination of AMW fractions of NOM. However, during chloramination, NOM fractions with AMW <2.5 kDa were found to produce higher concentrations of NDMA and total N-nitrosamines. The precursor materials of N-nitrosamines appeared to be more abundant in the low to medium MW fractions of NOM, which correspond to the fractions that are most difficult to remove using conventional drinking water treatment processes. Alternative or advanced treatment processes that target the removal of low to medium MW NOM including activated carbon adsorption, biofiltration, reverse osmosis, and nanofiltration, can be employed to minimise the formation of N-nitrosamines. [Copyright &y& Elsevier]

Abstract: N-Nitrosodimethylamine (NDMA) is known as the disinfection by-product and the pollutant in the source water. Reduction with zero-valent zinc (Zn(0)) was investigated as a potential technology to treat NDMA. The results showed that Zn(0) was effective for NDMA reduction at initial pH 7.0. There were lag period and rapid period during the process, the corresponding zero-order rate constant (k zero) was 2.968 ± 0.245 μg L−1 h−1 ([Zn(0)]0 = 10g L−1),the mass normalized pseudo-first-order rate (k M) was 0.1215 ± 0.0171 L g−1 h−1. The reactivity of zinc on NDMA removal was consistent with the zinc corrosion rate. NDMA had little effect on the corrosion of zinc. Lower solution pH benefited the reduction of NDMA with Zn(0). The consumption of the oxygen and the localized acidification should be the cause of the shift from lag to rapid reaction period in the aerobic experiments. 1,1-dimethylhydrazine (unsymmetrical dimethylhydrazine, UDMH), dimethylamine (DMA) were detected as the products of NDMA degradation. The nitrogen mass balance at 24 h was 56%, the loss can be due to the formation of ammonium, the degradation of UDMH and other unmeasured products. DMA formed during the degradation of UDMH with Zn(0), the nitrogen loss could be caused by the formation of unmeasured products. Catalytic hydrogenation is proposed to be the mechanism based on the results and the redox properties of zinc and NDMA. One reduction process is: the active hydrogen atoms initially cleave and reduce the N=O bond in NDMA, generating UDMH. Then the N–N bond in UDMH is cleaved to form DMA and ammonium. [Copyright &y& Elsevier]

Abstract: N-Nitrosamines, in particular N-nitrosodimethylamine (NDMA), are carcinogens, which occur as chlorine disinfection by-products (DBPs) in swimming pools and hot tubs. UV treatment is a commonly used technique in swimming pools for disinfection and DBP attenuation. UV irradiation is known to efficiently degrade N-nitrosamines. However, UV irradiation (at λ = 254 nm) of chlorinated dimethylamine (CDMA) and monochloramine, two NDMA precursors present in swimming pool water, resulted in a substantial UV-induced NDMA formation (∼1–2% molar yield based on initial CDMA concentration) simultaneously to NDMA photolysis. Maximum NDMA concentrations were found at UV doses in the range used for advanced oxidation (350–850 mJ cm−2). Very similar behaviour was found for other chlorinated secondary amines, namely diethylamine and morpholine. Effectiveness of UV irradiation for N-nitrosamine abatement depends on initial N-nitrosamine and precursor concentrations and the applied UV dose. N-Nitrosamine formation is hypothesized to occur via the reaction of nitric oxide or peroxynitrite with the secondary aminyl radical, which are products from the photolysis of monochloramine and chlorinated secondary amines, respectively. Experiments with pool water showed that similar trends were observed under pool water conditions. UV treatment (UV dose: ∼360 mJ cm−2) slightly increased NDMA concentration in pool water instead of the anticipated 50% abatement in the absence of NDMA precursors. [Copyright &y& Elsevier]

Abstract: N-Nitrosodimethylamine (NDMA) is a suspected human carcinogen that has recently been detected in wastewater, groundwater and drinking water. Treatment of this compound to low part-per-trillion (ng/L) concentrations is required to mitigate cancer risk. Current treatment generally entails UV irradiation, which while effective, is also expensive. The objective of this research was to explore potential bioremediation strategies as alternatives for treating NDMA to ng/L concentrations. Batch studies revealed that the propanotroph Rhodococcus ruber ENV425 was capable of metabolizing NDMA from 8 μg/L to <2 ng/L after growth on propane, and that the strain produced metabolites that do not pose a significant risk at the concentrations generated (). A laboratory-scale membrane bioreactor (MBR) was subsequently constructed to evaluate the potential for long-term ex situ treatment of NDMA. The MBR was seeded with ENV425 and received propane as the primary growth substrate and oxygen as an electron acceptor. At an average influent NDMA concentration of 7.4 μg/L and a 28.5 h hydraulic residence time, the reactor effluent concentration was 3.0 ± 2.3 ng/L (>99.95% removal) over more than 70 days of operation. The addition of trichloroethene (TCE) to the reactor resulted in a significant increase in effluent NDMA concentrations, most likely due to cell toxicity from TCE-epoxide produced during its cometabolic oxidation by ENV425. The data suggest that an MBR system can be a viable treatment option for NDMA in groundwater provided that high concentrations of TCE are not present. [ABSTRACT FROM AUTHOR]

The reactivity of permanganate with dimethylamine, as possible path of NDMA formation, has been investigated. The results have shown that potassium permanganate reaction with aqueous solutions of dimethylamine (DMA) leads to the formation of N-nitrosodimethylamine (NDMA). The contact time, the molar ratio of permanganate and DMA, pH and presence of nitrite are the key factors influencing the efficiency of NDMA formation. Significant conversion rates of DMA to NDMA were observed only for the high doses of permanganate, which were many times higher than those typically used in water treatment. This reaction however is of importance for water treatment technology, since it shows the possibility of NDMA formation as a result of oxidation of DMA. It is likely that nitrosation is the main path of the reaction. An important role of MnO2 suspension, formed as a result of permanganate reduction in NDMA formation is emphasized. Significant influence of MnO2 suspension on NDMA formation should draw our attention to the potential impact of MnO2 activated filtration beds on NDMA formation. [Copyright &y& Elsevier]

Ozonation of aqueous solutions of dimethylamine (DMA) leads to the formation of nitrosodimethylamine (NDMA). The yield of reaction is low (below 0.4% in relation to DMA) and increases with increasing pH. Contact time, ozone/DMA ratio and radical scavengers are other variables controlling the yield of reaction. Data from the literature and observed ozonation by-products suggest that nitrosation of DMA might be responsible for nitrosamine generation. NDMA can be recognized as a by-product of ozonation of DMA in water, which is formed in a specific, but reasonable, range of ozone/DMA ratios. The reaction may have potential importance for water treatment technology assuming reasonable micrograms per liter of DMA concentrations in raw waters. [Copyright &y& Elsevier]

N-nitrosodimethylamine (NDMA) is a potent carcinogen formed during chloramination of water and wastewater treatment plant effluents. A procedure is described for quantifying the concentration of the organic precursors of NDMA that could be formed during chlorination of wastewaters and natural waters. The method involves applying a high dose of monochloramine to a pH-buffered sample followed by a 10-day contact period, during which the monochloramine decays at a rate unrelated to the composition of the sample. Analyses of samples of municipal wastewater effluents and surface waters indicate that the method provides a robust and reproducible measurement of NDMA precursors over a wide range of conditions. A sensitive GC/CI/MS/MS analytical procedure for dimethylamine also is described and used to demonstrate that NDMA formation during chlorination of wastewater and natural waters cannot be explained by dimethylamine concentrations alone. [Copyright &y& Elsevier]

● nZVI/UV/PAA process was used to degrade spiramycin for the first time. ● 95.8% of PAA and 78.8% of H 2 O 2 were adopted in the nZVI/UV/PAA system. ● Degradation pathway of spiramycin was proposed and verified by DFT analysis. ● 65.2% of NDMA FP of spiramycin was reduced after nZVI/UV/PAA oxidation. ● The nZVI/UV/PAA process is a promising AOP for NDMA formation control. 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 H 2 O 2 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. [Display omitted] [ABSTRACT FROM AUTHOR]

• Chloramines were detected during chlorination of 18 compounds with alkylamine group. • The yields of chloramines are highly depended on the structure of precursors. • The reactivity of (CH 3) 2 NCl was similar to that of monochloramine. • (CH 3) 2 NCl at ppb level was observed in chlorinated natural water samples. Organic chloramines have attracted considerable attention because of their potential toxicity and reactivity. However, the lack of suitable and effective analytical methods has limited the study of organic chloramines due to their volatile and unstable properties. In this study, membrane introduction mass spectrometry (MIMS) combined with DPD/FAS titration was used to monitor the formation of organic chloramines. N-chlorodimethylamine [(CH 3) 2 NCl] and N-chlorodiethylamine [(C 2 H 5) 2 NCl] were detected and identified as the dominant volatile DBPs during chlorination of 18 organic compounds with dimethylamine or diethylamine functional groups, with yields ranging from 0.3% to 51.1% at a chlorine to precursor (Cl/P) molar ratio of 8.0. (CH 3) 2 NBr was formed in the presence of bromide, while the formation of (CH 3) 2 NCl was decreased. The reaction of phenol with (CH 3) 2 NCl combined with theoretical calculations confirmed that the reactivity of (CH 3) 2 NCl was similar to that of monochloramine. Moreover, (CH 3) 2 NCl and (C 2 H 5) 2 NCl were observed at the ppb level during chlorination of actual water samples collected from different areas. The results suggest that (CH 3) 2 NCl and (C 2 H 5) 2 NCl are important organic chloramines during chlorination, which may lead to the occurrence of further oxidation reactions and promote the formation of other disinfection byproducts simultaneously and should be of concern. [Display omitted] [ABSTRACT FROM AUTHOR]

• The contribution of DMF to NDMA FP was investigated in the aquatic environment • DMF was detected in influents of STPs with mass flux of 32.2–607 g/h • DMF was readily removed by biological treatment • STP effluent was an important source of DMF and NDMA FP in receiving rivers • DMF plays an important role in NDMA FP in surface waters The contribution of specific precursors to N -nitrosodimethylamine formation potential (NDMA FP) upon chloramination depends not only on their NDMA molar yields but also on their concentrations in the actual environment. We investigated the seasonal and diurnal patterns of the NDMA precursor N,N -dimethylformamide (DMF) and NDMA FP in the Yodo River basin, Japan, by examining water samples taken from inside the basin's largest sewage treatment plant (STP) as well as samples from five final effluents from four STPs, two main stream sites, and two tributary sites in the same basin. DMF and NDMA FP were found to be high in influent (raw sewage), and were found to be mostly removed during the STP treatment processes (especially with biological treatment). Nevertheless, DMF was found in concentrations of 0.06 to 31.7 µg/L in chlorinated effluents and in receiving rivers, while NDMA FP was detected in concentrations of 3.57 to 306 ng/L. Thus, STPs were shown to be an important source of DMF and NDMA FP to rivers. A strong positive correlation between NDMA FP and DMF was confirmed in the receiving river (K-M), indicating that DMF was an important NDMA precursor in the Yodo River basin. The contribution of DMF to NDMA FP was 15.8±11.2% (n = 4) in summer and 82.1±10.2% (n = 4) in winter in the main stream (site K-M) of the river due to insufficient dilution of chlorinated effluents from the largest STP. From the viewpoint of NDMA and NDMA FP control at downstream sites, monitoring and control of DMF at upstream sites are important. Image, graphical abstract [ABSTRACT FROM AUTHOR]

• AS properties and treatment conditions both affect the removal of NDMA precursors. • Biosorption is the most important removal mechanism of NDMA precursors. • Human urine is the main contributor to NDMA formation potential (FP) in effluents. • The removal of NDMA precursors by activated sludge (AS) depends on multiple factors. 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. Image, graphical abstract [ABSTRACT FROM AUTHOR]