Removal Of N-nitrosodimethylamine Research Articles

The role of Cu(II) in the reduction of N-nitrosodimethylamine with iron and zinc

The role of Cu(II) in the reduction of N-nitrosodimethylamine (NDMA) with zero-valent metals was investigated by determining the effects of Cu(II) on the removal, kinetics, products, and mechanism. NDMA removal was enhanced, and all reactions followed a pseudo-first-order kinetic model except for the Fe and Fe/0.1 mM Cu(II) systems. The iron mass-normalized pseudo-first-order rate constants (kMFe) increased with the Cu(II) concentration. The zinc mass-normalized pseudo-first-order rate constants (kMZn) were identical to those with the Cu(II) concentrations from 0.1 mM to 1.0 mM and were higher with 2.0 mM Cu(II). The types of products detected were unchanged. Some unknown products were also found. NDMA was reduced to 1,1-dimethylhydrazine (unsymmetrical dimethylhydrazine, UDMH). Then, UDMH was reduced into dimethylamine (DMA) by the Fe/Cu(II) and Zn/Cu(II) systems. Catalytic hydrogenation was proposed as the reduction mechanism. Several copper species, such as Cu(OH)2 in the Fe/Cu(II) system and Cu2O and Cu(OH)2 in the Zn/Cu(II) system enhanced NDMA reduction. Differences between the Fe/Cu(II) and Zn/Cu(II) systems were caused by the reduction potentials and surface conditions of the different metals and the copper species in the various systems.

Fate of NDMA precursors through an MBR-NF pilot plant for urban wastewater reclamation and the effect of changing aeration conditions

The removal of N-nitrosodimethylamine (NDMA) formation potential through a membrane bioreactor (MBR) coupled to a nanofiltration (NF) pilot plant that treats urban wastewater is investigated. The results are compared to the fate of the individual NDMA precursors detected: azithromycin, citalopram, erythromycin, clarithromycin, ranitidine, venlafaxine and its metabolite o-desmethylvenlafaxine. Specifically, the effect of dissolved oxygen in the aerobic chamber of the MBR pilot plant on the removal of NDMA formation potential (FP) and individual precursors is studied.During normal aerobic operation, implying a fully nitrifying system, the MBR was able to reduce NDMA precursors above 94%, however this removal percentage was reduced to values as low as 72% when changing the conditions to minimize nitrification. Removal decreased also for azithromycin (68–59%), citalopram (31–17%), venlafaxine (35–15%) and erythromycin (61–16%) on average during nitrifying versus non-nitrifying conditions. The removal of clarithromycin, o-desmethylvenlafaxine and ranitidine could not be correlated with the nitrification inhibition, as it varied greatly during the experiment time. The MBR pilot plant is coupled to a nanofiltration (NF) system and the results on the rejection of both, NDMA FP and individual precursors, through this system was above 90%.Finally, results obtained for the MBR pilot plant are compared to the percentage of removal by a conventional full scale biological wastewater treatment plant (WWTP) fed with the same influent. During aerobic operation, the removal of NDMA FP by the MBR pilot plant was similar to the full scale WWTP.

Degradation of N-nitrosodimethylamine (NDMA) and its precursor dimethylamine (DMA) in mineral micropores induced by microwave irradiation

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.

Sorption characteristics of N-nitrosodimethylamine onto biochar from aqueous solution

N-nitrosodimethylamine (NDMA) is an emerging carcinogenic disinfection by-product in water environment. Biochars utilized as sorbents for the removal of NDMA from aqueous solution, and the sorption characteristics and mechanism were investigate. Biochars were prepared from bamboo, rice straw and wood sawdust at 300–700°C. The pseudo-second-order model provided the best fit for the sorption kinetics of NDMA onto biochar and the sorption isotherms were described best with the Slips model. Biochar produced at 500°C removed NDMA from aqueous solution relatively efficiently, and the bamboo char demonstrated the best sorption potential among the three types of biochars. Solution chemistry such as pH and metal ions did not show obvious effect on NDMA removal. Three sorption mechanisms are suggested for NDMA sorption onto biochars, H-bond attraction between NO and the O-containing moieties, hydrophobic force between CH3 and the ordered graphitic structure, and partition process of NDMA into the non-carbonization part of biochar.

Enhanced photocatalytic performance of N-nitrosodimethylamine on TiO2 nanotube based on the role of singlet oxygen

N-nitrosodimethylamine (NDMA) photocatalytic degradation performance and mechanism were investigated on the TiO2 nanotube prepared from anatase TiO2 nanopowder in terms of the production of reactive oxygen species including hydroxyl radical, singlet oxygen and superoxide radical. Significantly higher NDMA degradation efficiency was obtained on anatase TiO2 nanotube rather than anatase TiO2 nanopowder. The tubular morphology may be responsible for almost 100% NDMA removal on TiO2 nanotube, presumably due to its confinement effect leading to NDMA molecules within the nanotube being attacked by reactive oxygen species such as hydroxyl radical and singlet oxygen, and initiating reaction inside the nanotube. In particular, the ability of the nanotubular structure of TiO2 nanotube to promote a singlet oxygen oxidation pathway contributes much to the enhanced NDMA degradation efficiency and favors the formation of dimethylamine and NO3−. Such function originating from nanotube morphology could bring new insights for the photocatalytic degradation of organic pollutants.

Water Quality Improvement by Combined UF, RO, and Ozone/Hydrogen Peroxide System (HiPOx) in the Water Reclamation Process

Conventional water reclamation processes, such as membrane bioreactors, are not always effective in removal of pharmaceuticals and personal care products (PPCPs), endocrine disrupting chemicals (EDCs) and/or N-nitrosodimethylamine (NDMA), even with the reverse osmosis (RO) membrane process. A study was conducted, at a NEWater factory in Singapore, to compare a conventional ultrafiltration (UF) membrane /RO treatment process with a treatment train having the HiPOx unit, an advanced oxidation process (AOP), which was installed between the UF and the RO unit operations. By incorporating the HiPOx into the UF/RO treatment process, following results were observed; 1) increased removal of PPCPs, EDCs and NDMA, 2) improvement in ultraviolet transmission (UVT) of the RO permeate, 3) enhanced removal of TOC and color, and increased UVT of the RO brine, 4) suppression of the increase in the RO transmembrane pressure by organic fouling.

상하수에서 N-Nitrosodimethylamine (NDMA) 발생 및 처리법 비교 분석

Overall studies for the N-nitrosodimethylamine (NDMA) formation and treatment methods were conducted. In this study, occurrence in several countries and emerging treatment technologies of NDMA were generally reviewed. The NDMA formation was dependent on pH, contact time, and molar ratio (monochloramine/dimethylamine). The formation was rapidly increased when the molar ratio was greater than 1. It was likely that monochloramine could be related to stimulate NDMA formation. NDMA concentrations in water supply and wastewater plants after disinfection were approximately 10 ng/L and 100 ng/L, respectively. UV oxidation and adsorption processes are regarded as effective technologies for the NDMA removal. It is suggested that the UV oxidation with proper lamps is applied in water supply system.

Occurrence and removal of N-nitrosodimethylamine and its precursors in wastewater treatment plants in and around Shanghai

Six wastewater treatment plants (WWTPs) were investigated to evaluate the occurrence and removal of N-nitrosodimethylamine (NDMA), NDMA formation potential (FP) and four specific NDMA precursors, dimethylamine (DMA), trimethylamine (TMA), dimethylformamide (DMFA) and dimethylaminobenzene (DMAB). DMA and tertiary amines with DMA functional group commonly existed in municipal wastewater. Chemically enhanced primary process (CEPP) had no effect on removal of either NDMA or NDMA FP. In WWTPs with secondary treatment processes, considerable variability was observed in the removal of NDMA (19%–85%) and NDMA FP (16%–76%), moreover, there was no definite relationship between the removal of NDMA and NDMA FP. DMA was well removed in all the six surveyed WWTPs; its removal efficiency was greater than 97%. For the removal of tertiary amines, biologic treatment processes with nitrification and denitrification had better removal efficiency than conventional activated sludge process. The best removal efficiencies for TMA, DMFA and DMAB were 95%, 68% and 72%, respectively. CEPP could remove 73% of TMA, 23% of DMFA and 36% of DMAB. After UV disinfection, only 17% of NDMA was removed due to low dosage of UV was applied in WWTP. Although chlorination could reduce NDMA precursors, NDMA concentration was actually increased after chlorination.

Molecular modeling of adsorbed NDMA and water in MFI zeolites

N-nitrosodimethylamine (NDMA), which is a carcinogenic and toxic N-nitrosamine, can be found in water resources associated with a multitude of processes in various industrial facilities or merely as a by-product of water or wastewater treatment. Therefore, the removal of NDMA from drinking water represents an important human safety and public health concern. The present paper presents a density functional theory study of NDMA adsorption in all-silica MFI, Na-ZSM-5 and H-ZSM-5 zeolites. The stability of NDMA inside the zeolite pores was investigated by calculating the amount of energy released during adsorption. Various configurations of adsorbed NDMA to the zeolites were investigated, predominantly at the intersection of straight and sinusoidal channels. The strength of the adsorption energies followed the order H-ZSM-5>Na-ZSM-5>all-silica MFI. NDMA has a dipole moment and the strongest binding of NDMA occurred through the interactions of the negatively charged O atom of the molecule to positive atoms of the zeolite. For comparison, similar calculations were performed for water adsorption in these three zeolites. The adsorption energy of water in these three structures followed the order Na-ZSM-5>H-ZSM-5>all-silica MFI. We also incorporated van der Waals corrections in the simulations, which had the effect of stabilizing NDMA within the zeolite channels, but did not significantly change the relative stability of the different adsorption geometries. It was concluded that H-ZSM-5 is a good candidate to remove NDMA. Finally, it should be pointed out that H-ZSM-5 has the largest difference in binding energy between NDMA and water of the studied zeolites, suggesting that separation of the two molecules is indeed feasible due to preferential interactions between zeolite and adsorbate molecule.

Reduction of N-Nitrosodimethylamine (NDMA) in Aqueous Solution by Nanoscale Fe/Al2(SO4)3

N-Nitrosodimethylamine (NDMA) is recently defined as one of nitrogenous disinfection by-products with high carcinogenicity and can be frequently detected in finished water. The decomposition of NDMA in water using nanoscale zero-valent iron (NZVI) in the presence of aluminum and iron salts was investigated in this paper. The results showed that some salts can enhance the removal of NDMA by commercial NZVI in the order of Al2(SO4)3 >> AlCl3 > FeSO4 > Na2SO4 ≈ NZVI alone, and the highest NDMA removal was 87.3 % in the presence of Al2(SO4)3. NDMA removal varied with the addition of Al2(SO4)3, NZVI dosage, initial NDMA concentration, solution pH, and temperature. The reduction of NDMA increased with the dosage of Al2(SO4)3 and NZVI, which follows a pseudo-first-order kinetics model. The removal of NDMA by NZVI was higher in acidic pHs than in alkaline ones, and the highest removal was found at pH 5. Higher reaction temperature can improve the removal of NDMA and reduce the reaction time. Based on the total nitrogen balance, most nitrogen of NDMA was converted to ammonium and dimethylamine.

The Review of NDMA Removal in Aqueous Solution

The paper is an overview of some new issues that are connected with the removal of N-Nitrosodimethylamine (NDMA) by some water technology. NDMA is the most frequently detected member of extremely carcinogens, the N-nitrosamines. In this paper, the recent new methods for removing NDMA are introduced and proposed the future direction of the research about the removal of NDMA.

Reduction of N-Nitrosodimethylamine with zero-valent zinc

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 (kzero) was 2.968 ± 0.245 μg L−1 h−1 ([Zn(0)]0 = 10g L−1),the mass normalized pseudo-first-order rate (kM) 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.

Performance of photocatalytic membrane reactor with dual function of microfiltration and organics removal

A nano-structured TiO2 membrane having desired pore structure has been prepared by the anodization treatment of micro-porous tubular type pure titanium filter. The anodized nano-structured TiO2 membrane was found to act as photocatalyst and decompose N-nitrosodimethylamine (NDMA) efficiently under UV irradiation. This UV/anodized TiO2 membrane process realized the complete removal of NDMA with 20 mg L−1 concentration, indicating that this process can be a promising technology for the purification of NDMA contaminated water.

Removal of refractory compounds by ultraviolet and anodized TiO2 metal membrane with reactive nano-sized cylindrical tubes on its surface

We investigated the treatment performance of conventional membrane separation, UV irradiation, UV/O3 system and UV/anodized TiO2 membrane technology for the removal of N-Nitrosodimethylamine (NDMA) from water. The RO membrane did not prove to be effective for NDMA removal. The UV/anodized TiO2 membrane process decomposed almost 100% of NDMA in the range of all NDMA concentrations. UV/A-Ti-M system was achieved the complete removal of NDMA within 20 mg l-1 of NDMA concentration, indicating that the UV/ anodized TiO2 membrane process is a promising treatment technology for treating NDMA contaminated water. With regards to by-products, DMA yield increased with an increase in initial NDMA concentration, whereas MA yield decreased.

Fate of N-nitrosodimethylamine, trihalomethane and haloacetic acid precursors in tertiary treatment including biofiltration

The presence of disinfection by-products (DBPs) such as trihalomethanes (THMs), haloacetic acids (HAAs) and N-nitrosamines in water is of great concern due to their adverse effects on human health. In this work, the removal of N-nitrosodimethylamine (NDMA), total THM and five HAA precursors from secondary effluent by biological activated carbon (BAC) is investigated at full and pilot scale. In the pilot plant two filter media, sand and granular activated carbon, are tested. In addition, we evaluate the influence of ozonation prior to BAC filtration on its performance. Among the bulk of NDMA precursors, the fate of four pharmaceuticals containing a dimethylamino moiety in the chemical structure are individually investigated. Both NDMA formation potential and each of the studied pharmaceuticals are dramatically reduced by the BAC even in the absence of main ozonation prior to the filtration. The low removal of NDMA precursors at the sand filtration in comparison to the removal of NDMA precursors at the BAC suggests that adsorption may play an important role on the removal of NDMA precursors by BAC. Contrary, the precursors for THM and HAA formation are reduced in both sand filtration and BAC indicating that the precursors for the formation of these DBPs are to some extent biodegradable.

Removal of N-nitrosodimethylamine by ultraviolet treatment and anodizing TiO2 membrane processes

N-Nitrosodimethylamine (NDMA) is a disinfectant by-product shown to be carcinogenic, mutagenic, and teratogenic. The objective of this study is to compare NDMA removal efficiencies in water using conventional technologies (microfiltration, nanofiltration, reverse osmosis, and UV treatment) and innovative hybrid technology, which combines UV treatment with anodizing TiO2 membrane (UV/A-Ti-M) technology. In the UV/A-Ti-M photoreaction, the affecting factors such as UV intensity, the initial concentration of NDMA, and initial pHs were investigated. Even though membrane processes were ineffective in removing NDMA compounds, UV irradiation used in combination with an anodizing TiO2 membrane were achieved to remove NDMA completely from water. When NDMA was decomposed by UV/A-Ti-M process, dimethylamine yield increased and methylamine yield decreased with an increase in initial NDMA concentration. The successful removal of NDMA was specific to acidic conditions (pH 4–6). UV/A-Ti-M process is useful and powerful tools to remove NDMA in water. © 2011 American Institute of Chemical Engineers Environ Prog, 2011

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.

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.

Effects of Primary Substrate Concentration on NDMA Transport during Simulated Aquifer Recharge

N-nitrosodimethylamine (NDMA) is known to be highly carcinogenic and is present in drinking water, wastewater, and a variety of foods. Because of its presence in chloraminated water at nanogram per liter concentrations, NDMA has become an emerging issue for reclaimed water which may be used for aquifer recharge or irrigation. This research investigated the fate of NDMA in two soil column systems used to simulate subsurface transport. One column system was operated under aerobic conditions with increasing primary substrate concentration where the biodegradable organic carbon (BDOC) in reclaimed water was used as the primary substrate. The reclaimed water content in the influent was increased from 0 to 25% in the column to increase the BDOC concentration. Negligible NDMA removal was observed at 0% reclaimed water and increasing the primary substrate in the influent resulted in NDMA removal suggesting that biodegradation of NDMA might be a cometabolic process. The effects of redox conditions on NDMA fate was studied by operating a second column system with 100% reclaimed water under anoxic conditions and then changing the conditions to aerobic. It was observed that NDMA removal was similar under both aerobic and anoxic condition, however, much lower effluent concentrations were observed under aerobic conditions. Under anoxic condition, a normalized mass removal rate of 254 ng NDMA/mg DOC was observed which increased to 273-ng NDMA/mg DOC under aerobic conditions. The majority of NDMA and substrate removal occurred in the first of three columns in series column under both aerobic and anoxic conditions. Normalized mass removal rates of NDMA after the first, second, and third columns were 372, 30, and 20 ng NDMA/mg DOC, respectively. Since the majority of dissolved organic carbon was also removed in the first column, NDMA biodegradation was consistent with cometabolic activity. Batch tests verified the biodegradation removal potential of NDMA. Addition of a methylotrophic substrate, methanol and an aromatic substrate, toluene, did not increase NDMA removal.

Monitoring the prevalence of nitrosamines in South African waters and their removal using cyclodextrin polyurethanes

The prevalence of nitrosamines, especially N-nitrosodimethylamine (NDMA), was monitored in three South African water supplies. NDMA a disinfection by-product (DBP) and potent carcinogen, has recently been detected in many drinking water supplies internationally. Besides direct industrial or human-derived contamination, nitrosodimethylamine can be formed through a chemical reaction between monochloroamine and an organic based compound such as dimethylamine which is frequently detected in surface water. It has been suggested that chloramination of surface waters with a high concentration of dissolved organic carbon (DOC) could result in elevated NDMA formation. Growing evidence suggests that NDMA occurs more frequently and at higher concentrations in drinking water systems that practise chloramination compared to systems that use chlorination. In gauging the extent of water contamination by nitrosamines in water distribution systems, especially NDMA, water samples collected from three different water treatment plants that practise chemical drinking water disinfection were qualitatively analysed for the presence of nitrosamines. Solid phase microextraction (SPME) was employed in the extraction of nitrosamines from the water samples and gas chromatography–mass spectrometry (GC–MS), was used in the analysis of the water samples. Trace amounts of NDMA were detected at one of the water treatment plants and in the distribution network. The application of water-insoluble cyclodextrin (CD) polymers in the removal of nitrosamines and potential amine precursors from the water samples was tested. Quantitative removal of NDMA (based on peak area) from the water samples was achieved which suggests that in the water treatment train the use of these nanosponges can be applied in the mitigation of trace contaminants such as NDMA.