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.     

Predicting disinfection by-product formation potential in water

Formation of regulated and non-regulated disinfection by-products (DBPs) is an issue at both potable water and wastewater treatment plants (W/WWTPs). Water samples from W/WWTPs across the USA were collected and DBP formation potentials (DBPFPs) in the presence of free chlorine and chloramine were obtained for trihalomethane (THM), haloacetic acid (HAA), haloacetonitrile (HAN), and N-nitrosodimethylamine (NDMA). With nearly 200 samples covering a range of dissolved organic carbon (0.6-23 mg/L), ultraviolet absorbance (0.01-0.48 cm⁻¹ at 254 nm wavelength), and bromide (0-1.0 mg/L) levels, power function models were developed to predict the carbonaceous DBP (C-DBP) and nitrogenous DBP (N-DBP) precursors spanning 3 orders of magnitudes. The predicted THM and HAA formation potentials fitted well with the measured data (analytical variance of less than 22%). Inclusion of dissolved organic nitrogen (DON) into the HANFP model improved the predictions. NDMAFP was the most difficult one to predict based upon the selected water quality parameters, perhaps suggesting that bulk measurements such as DOC or UVA₂₅₄ were not appropriate for tracking NDMAFP. These are the first such DBPFP models for wastewater systems, and among the few models that consider both C-DBPs and N-DBPs formation potentials from the same water sources.     

体外模拟亚硝化体系中优选阻断NDMA生成的香辛料精油复合抑制剂

为了有效抑制N-二甲基亚硝胺(N-nitrosodimethylamine,NDMA)的形成,在体外模拟亚硝化反应体系中,先通过单因素实验研究市售常见的9种香辛料精油对NDMA的抑制作用,再利用二次回归正交组合试验设计,筛选最佳精油复合抑制剂配比。结果表明,9种香辛料精油对NDMA的形成均有抑制作用,二次回归正交组合设计得到的最优复合配比是胡椒2.078 mL/L、姜汁3.118 mL/L、花椒3.692 mL/L、八角2.833 mL/L和丁香0.218 mL/L,该条件下NDMA的抑制率为64.412%±0.25%。     

Field evidence of biodegradation of N-Nitrosodimethylamine (NDMA) in groundwater with incidental and active recycled water recharge

Biodegradation of N-Nitrosodimethylamine (NDMA) has been found through laboratory incubation in unsaturated and saturated soil samples under both aerobic and anaerobic conditions. However, direct field evidence of in situ biodegradation in groundwater is very limited. This research aimed to evaluate biodegradation of NDMA in a large-scale groundwater system receiving recycled water as incidental and active recharge. NDMA concentrations in 32 monitoring and production wells with different screen intervals were monitored over a period of seven years. Groundwater monitoring was used to characterize changes in the magnitude and extent of NDMA in groundwater in response to seasonal hydrogeologic conditions and, more importantly, to significant concentration variations in effluent from water reclamation plants (associated with treatment-process changes). Extensive monitoring of NDMA concentrations and flow rates at effluent discharge locations and surface-water stations was also conducted to reasonably estimate mass loading through unlined river reaches to underlying groundwater. Monitoring results indicate that significant biodegradation of NDMA occurred in groundwater, accounting for an estimated 90% mass reduction over the seven-year monitoring period. In addition, a discrete effluent-discharge and groundwater-extraction event was extensively monitored in a well-characterized, localized groundwater subsystem for 626 days. Analysis of the associated NDMA fate and transport in the subsystem indicated that an estimated 80% of the recharged mass was biodegraded. The observed field evidence of NDMA biodegradation is supported by groundwater transport modeling accounting for various dilution mechanisms and first-order decay for biodegradation, and by a previous laboratory study on soil samples collected from the study site [Bradley, P.M., Carr, S.A., Baird, R.B., Chapelle, F.H., 2005. Biodegradation of N-Nitrosodimethylamine in soil from a water reclamation facility. Bioremediat. J. 9 (2), 115-120.].     

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

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

Occurrence and formation potential of N-nitrosodimethylamine in ground water and river water in Tokyo

N-nitrosodimethylamine (NDMA), a disinfection byproduct of water and wastewater treatment processes, is a potent carcinogen. We investigated its occurrence and the potential for its formation by chlorination (NDMA-FP_2Cl) and by chloramination (NDMA-FP_2NHCl) in ground water and river water in Tokyo. To characterize NDMA precursors, we revealed their molecular weight distributions in ground water and river water. We collected 23 ground water and 18 river water samples and analyzed NDMA by liquid chromatography-tandem mass spectrometry. NDMA-FP_2Cl was evaluated by chlorinating water samples with free chlorine for 24 h at pH 7.0 while residual free chlorine was kept at 1.0-2.0 mgCl₂/L. NDMA-FP_2NHCl was evaluated by dosing water samples with monochloramine at 140 mgCl₂/L for 10 days at pH 6.8. NDMA precursors and dissolved organic carbon (DOC) were fractionated by filtration through 30-, 3-, and 0.5 kDa membranes. NDMA concentrations were <0.5-5.2 ng/L (median: 0.9 ng/L) in ground water and <0.5-3.4 ng/L (2.2 ng/L) in river water. NDMA concentrations in ground water were slightly lower than or comparable to those in river water. Concentrations of NDMA-FP_2Cl were not much higher than concentrations of NDMA except in samples containing high concentrations of NH₃ and NDMA precursors. The increased NDMA was possibly caused by reactions between NDMA precursors and monochloramine unintentionally formed by the reaction between free chlorine and NH₃ in the samples. NDMA precursors ranged from 4 to 84 ng-NDMA eq./L in ground water and from 11 to 185 ng-NDMA eq./L in river water. Those in ground water were significantly lower than those in river water, suggesting that NDMA precursors were biodegraded, adsorbed, or volatilized during infiltration. The molecular weight of NDMA precursors in river water was dominant in the <0.5 kDa fraction, followed by 0.5-3 kDa. However, their distribution was inconsistent in ground water: one was dominant in the <0.5 kDa fraction, and the other in 0.5-3 kDa. Molecular weight distributions of NDMA precursors were very different from those of DOC. This is the first study to reveal the widespread occurrence and characterization of NDMA precursors in ground water.     

Occurrence and control of nitrogenous disinfection by-products in drinking water--a review

The presence of nitrogenous disinfection by-products (N-DBPs), including nitrosamines, cyanogen halides, haloacetonitriles, haloacetamides and halonitromethanes, in drinking water is of concern due to their high genotoxicity and cytotoxicity compared with regulated DBPs. Occurrence of N-DBPs is likely to increase if water sources become impacted by wastewater and algae. Moreover, a shift from chlorination to chloramination, an option for water providers wanting to reduce regulated DBPs such as trihalomethanes (THMs) and haloacetic acids (HAAs), can also increase certain N-DBPs. This paper provides a critical review of the occurrence and control of N-DBPs. Data collated from surveys undertaken in the United States and Scotland were used to calculate that the sum of analysed halonitromethanes represented 3-4% of the mass of THMs on a median basis; with Pearson product moment correlation coefficients of 0.78 and 0.83 between formation of dihaloacetonitriles and that of THMs and HAAs respectively. The impact of water treatment processes on N-DBP formation is complex and variable. While coagulation and filtration are of moderate efficacy for the removal of N-DBP precursors, such as amino acids and amines, biofiltration, if used prior to disinfection, is particularly successful at removing cyanogen halide precursors. Oxidation before final disinfection can increase halonitromethane formation and decrease N-nitrosodimethylamine, and chloramination is likely to increase cyanogen halides and NDMA relative to chlorination.     

Breakpoint chlorination and free-chlorine contact time: implications for drinking water N-nitrosodimethylamine concentrations

North American drinking water utilities are increasingly incorporating alternative disinfectants, such as chloramines, in order to comply with disinfection by-product (DBP) regulations. N-Nitrosodimethylamine (NDMA) is a non-halogenated DBP, associated with chloramination, having a drinking water unit risk two to three orders of magnitude greater than currently regulated halogenated DBPs. We quantified NDMA from two full-scale chloraminating water treatment plants in Alberta between 2003 and 2005 as well as conducted bench-scale chloramination/breakpoint experiments to assess NDMA formation. Distribution system NDMA concentrations varied and tended to increase with increasing distribution residence time. Bench-scale disinfection experiments resulted in peak NDMA production near the theoretical monochloramine maximum in the sub-breakpoint region of the disinfection curve. Breakpoints for the raw and partially treated waters tested ranged from 1.9:1 to 2.4:1 (Cl(2):total NH(3)-N, M:M). Bench-scale experiments with free-chlorine contact (2h) before chloramination resulted in significant reductions in NDMA formation (up to 93%) compared to no free-chlorine contact time. Risk-tradeoff issues involving alternative disinfection methods and unregulated DBPs, such as NDMA, are emerging as a major water quality and public health information gap.     

A nationwide survey of NDMA in raw and drinking water in Japan

A nationwide survey of N-nitrosodimethylamine (NDMA) in both raw and finished water samples from drinking water treatment plants (DWTPs) in Japan was conducted. NDMA was analyzed by solid-phase extraction (SPE) followed by ultra performance liquid chromatography (UPLC) coupled with tandem mass spectrometry (MS/MS). NDMA was detected in 15 of 31 raw water samples collected in the summer at concentrations up to 2.6 ng/L, and in 9 of 28 raw water samples collected in winter at concentrations up to 4.3 ng/L. The NDMA concentrations were higher in raw water samples collected from treatment plants with catchment areas that have high population densities. The NDMA concentrations were higher in river water samples collected from the east and west of Japan than in those collected from other areas. NDMA was detected in 10 of 31 finished samples collected in summer at reduced concentrations of up to 2.2 ng/L, while 5 of 28 finished samples collected in winter showed NDMA concentrations up to 10 ng/L. The highest NDMA levels were detected in finished water samples collected from the Yodo River basin DWTP, which uses ozonation. Furthermore, evaluation of the process water produced at six advanced water treatment plants was conducted. Influent from the Yodo River indicated that the NDMA concentration increased during ozonation to as high as 20 ng/L, and then decreased with subsequent biological activated carbon treatment. To our knowledge, this is the first nationwide evaluation of NDMA concentrations in water conducted in Japan to date.     

氧原子对二甲基亚硝胺羟基化反应的机理研究

用量子化学密度泛函（DFT）方法,在B3LYP／6—31G＊＊水平下,研究了氧原子对二甲基亚硝胺（NDMA）羟基化的反应机理。结果表明,氧原子对NDMA甲基上CH键的直接氧化过程,比经单一三交叉点的反应路径要容易的多。反应势能面进一步说明,氧化方式下的羟基化反应是容易进行的放热反应;溶剂化效应和MP2／6—311G＊＊更高级别的计算,不改变其反应机理,只改变了活化能的大小。