Removal Of N-nitrosamines Research Articles

Complete removal of N-nitrosamines using in-situ constructed sequential microreactors: Synergies of catalysis-adsorption between N-nitrosamines and their degradation products

The removal of N-nitrosamines from water faces the challenges of their difficult adsorption, and incomplete mineralization of degradation products. Herein, we report a new strategy by in-situ constructing microreactor on carbon cloth arrayed CoNi spinel oxide through membrane encapsulation. The NiCo2O4-nanoarrays activate peroxonosulfate, generating reactive oxygen species that rapidly degrade N-nitrosamines. The breaking N-N bond of N-nitrosamines provides an effective binding site for adsorbing degradation products (secondary amines). Meanwhile, electrons conducted from secondary amines adsorbed on Ni sites reconstruct the charge of CoNi sites, bolstering the peroxonosulfate activation to further remove N-nitrosamines and secondary amines. Moreover, the microreactive interface formed between membrane substrate and NiCo2O4-nanoarrays improved the reaction efficiency. It maintains efficient N-nitrosamines removal (96–99%) even in the presence of humic acid. Actual wastewater experiments confirmed its effective control of both N-nitrosamines and N-nitrosodimethylamine formation potential. This study provides a novel approach for eliminating the risk of N-nitrosamines in water.

Cyclic coupling of photocatalysis and adsorption for completely safe removal of N-nitrosamines in water

The incomplete removal of N-nitrosamines in water through current degraded techniques and the carcinogenicity of N-nitrosamines call for alternative complete and safe removal approaches. Here, we describe a cyclic coupling process of photocatalysis and adsorption enabling N-nitrosamines in water thoroughly and safely removed. Among them, the immobilized TiO2/Ti photocatalyst degraded N-nitrosamines into primary and secondary amines up to 100% by attacking on nitrosyl nitrogen via •OH originated from its nanowire film morphology. Furthermore, the affinity of HY zeolite to primary and secondary amines led to efficient adsorption through corresponding to Lagergren adsorption rate equation of second order. And then the cyclic coupling process of photocatalysis and adsorption realized complete and safe removal of N-nitrosamines with various concentration ranging from 0.1 mM to 1 mM in water, significantly higher than the existing reports on the removal rate of N-nitrosamines and the formation potential of N-nitrosamines. This study will lead to new avenues for complete and safe eliminaton of hardly degradable hazardous substances in water.

Degradation of N-nitrosamines and 1,4-dioxane using vacuum ultraviolet irradiation (UV254+185 nm or UV172 nm)

Advanced oxidation processes (AOPs) play a vital role in attenuating contaminants of emerging concern (CECs) during potable water reuse. AOPs are conventionally performed by irradiating with a 254-nm low-pressure (LP) mercury-vapor (Hg) ultraviolet (UV) lamp along with chemical treatment. Compared with UV-C light treatment (200–280 nm), vacuum-UV (V-UV) light treatment (100–200 nm) is advantageous in terms of hydroxyl radical generation without the requirement for chemical treatment. This study assessed the potential of V-UV (172-nm Xe2 excimer or 185 + 254-nm LP-Hg) lamps on the destruction of two major CECs in potable water reuse, namely N-nitrosodimethylamine (NDMA) and 1,4-dioxane. Direct irradiation using UV254 nm or UV185+254 nm lamps achieved ≥94% removal of N-nitrosamines, including NDMA, at a UV dose of 900 mJ/cm2. In contrast, the Xe2 excimer lamp (UV172 nm) was less effective for N-nitrosamine removal, achieving up to 82% removal of NDMA. The removal of 1,4-dioxane by V-UV lamps at a UV dose of 900 mJ/cm2 reached 51% (UV172 nm) and 28% (UV185+254 nm), both of which results were superior to that obtained using a conventional UV254 nm lamp (10%). The addition of hydrogen peroxide during UV254 nm or UV185+254 nm irradiation was found to enhance the removal of 1,4-dioxane, while UV172 nm irradiation without hydrogen peroxide addition still exhibited greater efficiencies than those UV254 nm lamps-based AOPs. Overall, this study demonstrated that the removal of both NDMA and 1,4-dioxane can be successfully achieved using either a UV254+185 nm lamp with hydrogen peroxide or a UV172 nm Xe2 excimer lamp without hydrogen peroxide.

Occurrence and Removal of N-nitrosamines in the Wastewater Treatment Plants Using Different Treatment Processes

This study measured the concentrations of six N-nitrosamines (NAs) in water samples from each process stage of three wastewater treatment plants (WWTPs) and their corresponding receiving rivers. The occurrence and removal of NAs was then systematically studied in three WWTPs using different treatment processes, and their pollution profiles and sources in the receiving rivers were analyzed. The results showed that the six NAs occurred widely in the wastewater from every process stage of three WWTPs. NPIP, NDMA, and NPYR were the dominant pollutants with concentrations in the tens to hundreds ng·L-1. The three WWTPs using different treatment processes removed a certain amount of NAs, and the modified A2/O and A2/O+MBR showed good NAs removal effects, with total removal rates of 95% and 63%, respectively. The removal of NAs mainly relied on microbial degradation and transformation during the biochemical stage. During the filtration, disinfection, and MBR stages, NAs precursors in the wastewater treatment system could form some added NAs after a series of reactions. The six NAs were also frequently detected in the surface waters of receiving rivers, where the main pollutants were also MDMA, NPIP, and NPYR, which was consistent with the influent of the WTTPs. The sources of NAs in the receiving rivers were wide ranging and complicated, including emission from the effluent of the WTTPs, the release of untreated sanitary sewage, industrial wastewater, and surface runoff from industrial districts. Therefore, effective measures should be taken to reduce the input of NAs into receiving rivers, such as enhancing the capacity of sewage collection and treatment and optimizing sewage treatment processes.

Toward N-nitrosamines free water: Formation, prevention, and removal

ABSTRACTThis study elucidates the recent trends in the formation, prevention, and removal of N-nitrosamines such as N-nitrosodimethylamine (NDMA) from wastewater or drinking water. Reports are rife on the occurrence of NDMA in areas such as amine degradation during postcombustion CO2 capture (PCC), chlorinated/chloraminated and ozonated drinking water, smoked or cooked foods personal care, tobacco and pharmaceutical products. The major routes responsible for the formation of NDMA in portable waters include chlorination/chloramination and ozonation. The major NDMA precursors are secondary, tertiary, and quaternary amines such as dimethylamine, diethanolamine, and triethanolamine. Due to the environmental and public health concerns posed by this contaminant, a proactive approach is necessary towards suppressing their occurrence, as well as their removal. Consequently, this study critically reviewed the formation, prevention, and removal of N-nitrosamines. The study discussed NDMA prevention techniques, such as physical adsorption, pre-oxidation, and biological activated carbon. The removal techniques discussed here include physicochemical (such as combined adsorption and microwave irradiation and UV photolysis), bioremediation, catalytic reduction, and dope technology. Irrespective of the effectiveness and seemingly economic viability of some of these technologies, preventing the occurrence of NDMA right from the outset is more potent because the treatments consume more energy.

High rejection reverse osmosis membrane for removal of N-nitrosamines and their precursors.

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.

Removal of N-nitrosamines in a membrane bioreactor and nanofiltration hybrid system for municipal wastewater reclamation: Process efficiency and mechanisms

This study investigated the removal efficiency and mechanisms of water contaminants (mainly N-nitrosamines) during municipal wastewater reclamation by a membrane bioreactor (MBR) and nanofiltration (NF) hybrid system. The removal of bulk water contaminants was governed by the microbial activities in the MBR and molecular weight cut-off (MWCO) of the NF membranes. The removal of N-nitrosamines by the MBR was primarily attributed to biodegradation by aerobic bacteria, which can be determined by the reactivity of the amine functional groups with the catabolic enzymes (removal efficiency=45–84%). Adsorption and formation of membrane fouling can enhance the removal of N-nitrosamines by the NF membranes. However, size-exclusion is found to play a major role in the removal of N-nitrosamines by the NF membranes since the removal efficiencies of N-nitrosamines varied significantly depending on molecular weight of the N-nitrosamines and MWCO of the NF membranes (removal efficiency: NE90>NE70).

Cleaning carcinogenic nitrosamines with zeolites

N-nitrosamines are characterized with an N-nitroso group N–NO. N-nitrosamines are strong carcinogens or potent carcinogens. Nitrosamines occur widely in the environment, e.g., as tobacco smoke that causes cancers of lungs, larynx, oral cavity and pharynx, pancreas, kidney and bladder. It is difficult to capture selectively N-nitrosamines in the environment. Therefore, zeolite, which is a molecular sieve, may help to sequester N-nitrosamines. Zeolites are a class of aluminosilicates, characterized by ordered microporous structures with acidic–basic sites on the surface and energetic field inside the pores. They have been widely applied in industry as adsorbents and catalysts because of their unique shape selectivity. Here, we review the latest research on adsorption and catalytic degradation of N-nitrosamines by zeolite materials. The efficiency of zeolite is increased using metal oxides. Removal of N-nitrosamines in smoke is discussed.

N-nitrosamine rejection by reverse osmosis: Effects of membrane exposure to chemical cleaning reagents

The impact of chemical cleaning on the removal of N-nitrosamines by low pressure reverse osmosis (RO) membranes was investigated. The results show that caustic chemical cleaning resulted in an increase in membrane permeability but caused a notable decrease in the rejection of N-nitrosamines. The impact of caustic chemical cleaning was particularly obvious for N-nitrosodimethylamine (NDMA) and N-nitrosomethylethylamine (NMEA), which have the lowest molecular weight amongst the N-nitrosamines investigated in this study. A correlation between the increase in permeability and the decrease in the rejection of either NDMA or NMEA could be observed. The rejection of conductivity also decreased as the membrane permeability increased, indicating that conductivity rejection can be an indicative parameter of predicting changes in NDMA and NMEA rejection during RO plant operation. The impact of caustic cleaning was not permanent and could be significantly reduced by a subsequent acidic cleaning step.

Occurrence and fate of N-nitrosamines and their formation potential in three wastewater treatment plants in Japan

N-nitrosamines are well known as carcinogens present in the environment. However, studies of the occurrence and fate of N-nitrosamines and their N-nitrosamine formation potential (FP) in wastewater treatment plants (WWTPs) are lacking. Therefore, the objectives of this study were to determine the occurrence of N-nitrosamines in WWTPs, the FP of N-nitrosamines on chloramination during wastewater treatment, and the efficiency of FPNH2Cl reduction by biological treatment. Also, the residual FPNH2Cl in the final discharge was investigated. The efficiencies of removal of N-nitrosamines ranged from 35 to 94% (WWTP O; residential area), from 58 to 98% (WWTP E; industrial area), and from 58% to >99% (WWTP N; industrial area). In WWTP O, the rates of production of N-nitrosodimethylamine (NDMA) (42%) and NDBA (58%) were the highest. In WWTP E, only NDBA (34%) was produced. In WWTP N, NPYR and NPIP (both >99%) were produced. NDMA FPNH2Cl values were very high in influent in all WWTPs. The efficiencies of removal of N-nitrosamine FPNH2Cl during biological treatment ranged from 20% to >99%, but there is no obvious explanation for this variability. Residual N-nitrosamine FPNH2Cl ranged from 2 to 22 ng L(-1). Thus, N-nitrosamines could be produced in water purification or reclamation plants using discharge from WWTPs.

Removal of N-nitrosamines by an aerobic membrane bioreactor

This study investigated the fate of eight N-nitrosamines during membrane bioreactor (MBR) treatment. The results suggest that biodegradation is mainly responsible for the removal of N-nitrosamines during MBR treatment. Other removal mechanisms were insignificant (e.g. adsorption to sludge) or not expected (e.g. photolysis and volatilization) given the experimental conditions and physicochemical properties of the N-nitrosamines studied here. N-nitrosamine removal efficiencies were from 24% to 94%, depending on their molecular properties. High removal of N-nitrosamines such as N-nitrosodimethylamine and N-nitrosodiethylamine could be explained by the presence of strong electron donating functional groups (EDG) in their structure. In contrast, N-nitrosomorpholine possessing the weak EDG morpholine was persistent to biodegradation. The removal efficiency of N-nitrosomorpholine was 24% and was the lowest amongst all N-nitrosamines investigated in this study.

Investigation of removal of N-nitrosamines and their precursors in water treatments using activated carbon nanoparticles

N-nitrosamines have been detected in various water types. A strategy for removal of this group of compounds should be taken to reduce the health risks for humans. In this study, a fast and sensitive LC-MS/MS method was developed for quantitative analysis of nine N-nitrosamines and four precursors in a single sample. The Method Detection Limits (MDLs) in natural water ranged from 0.05 μg/L to 5 μg/L without using SPE pre-concentration. Three different types of activated carbon nanoparticles (NPs) (bamboo, charcoal and coconut shell as raw materials) were used to carry out removal experiments in two different pHs (pH 6.6 and 8.6). The results indicated that coconut shell-based activated carbon NPs had higher removal efficiency than the other two with a typical dosage of activated carbon NPs, at a typical contact time of 4 hours. No significant differences in removal efficiency between the two selected pH values were observed.

Removal of N-Nitrosamines and Their Precursors by Nanofiltration and Reverse Osmosis Membranes

Rejection of selected N -nitrosamines, a group of probable human carcinogens, and their precursors by nanofiltration (NF) and brackish water reverse osmosis (BWRO) membranes was evaluated using a bench-scale cross-flow filtration apparatus. The tested nitrosamines included N -nitrosodimethylamine, N -nitrosomethylethylamine, N -nitrosopyrrolidine, N -nitrosodiethylamine, N -nitrosodi- n -propylamine, and N -nitrosodi- n -butylamine. The target nitrosamine precursors included secondary amines such as dimethylamine, methylethylamine, diethylamine, and dipropylamine. Rejection of nitrosamines varied greatly depending on the tested membranes (9–75% for NF membranes and 54–97% for BWRO membranes) and the molecular weight of nitrosamines. Experimental data obtained with the BWRO membranes matched well with an irreversible thermodynamic model coupled with film theory. The model further suggested that effective diffusion of nitrosamines through the BWRO membranes is responsible for the relatively low rejections o...

Occurrence and removal of N-nitrosamines in wastewater treatment plants

The presence of nitrosamines in wastewater might pose a risk to water resources even in countries where chlorination or chloramination are hardly used for water disinfection. We studied the variation of concentrations and removal efficiencies of eight N-nitrosamines among 21 full-scale sewage treatment plants (STPs) in Switzerland and temporal variations at one of these plants. N-nitrosodimethylamine (NDMA) was the predominant compound in STP primary effluents with median concentrations in the range of 5–20 ng/L, but peak concentrations up to 1 μg/L. N-nitrosomorpholine (NMOR) was abundant in all plants at concentrations of 5–30 ng/L, other nitrosamines occurred at a lower number of plants at similar levels. From concentrations in urine samples and domestic wastewater we estimated that human excretion accounted for levels of <5 ng/L of NDMA and <1 ng/L of the other nitrosamines in municipal wastewater, additional domestic sources for <5 ng/L of NMOR. Levels above this domestic background are probably caused by industrial or commercial discharges, which results in highly variable concentrations in sewage. Aqueous removal efficiencies in activated sludge treatment were in general above 40% for NMOR and above 60% for the other nitrosamines, but could be lower if concentrations were below 8–15 ng/L in primary effluent. We hypothesize that substrate competition in the cometabolic degradation explains the occurrence of such threshold concentrations. An additional sand filtration step resulted in a further removal of nitrosamines from secondary effluents even at low concentrations. Concentrations released to surface waters were largely below 10 ng/L, suggesting a low impact on Swiss water resources and drinking water generation considering the generally high environmental dilution and possible degradation. However, local impacts in case a larger fraction of wastewater is present cannot be ruled out.

Fate and Transport of N‐Nitrosamines Under Conditions Simulating Full‐Scale Groundwater Recharge Operations

The key objective of this study was to investigate the attenuation mechanisms of seven N-nitrosamine compounds at environmental concentrations and under conditions relevant to groundwater recharge operations. The study used a combination of controlled laboratory-scale soil-column experiments and groundwater monitoring at a full-scale river-bank filtration facility. Findings of the controlled column experiments suggest that N-nitrosodimethylamine and six other N-nitrosamines (N-nitrosodiethylamine, N-nitrosomethylethylamine, N-nitroso-n-propylamine, N-nitrosodi-n-butylamine, N-nitrosopiperidine, and N-nitrosopyrrolidine) are biodegradable under oxic and anoxic oxidation-reduction conditions. Half lives determined in this study for the targeted compounds varied between 1.3 and 7 days, which will ensure a removal to below detection limits (< 2 ng/L) within short travel times in groundwater recharge systems. Findings of this study suggest that complete removal of N-nitrosamines requires the presence of an adapted biocommunity, which will be established over several weeks to months.