Ozonation of N-Nitrosamines in the Reverse Osmosis Concentrate from Water Recycling Applications

This study aims to evaluate the performance of ozone treatment for removing N-nitrosamines from reverse osmosis (RO) concentrate in water recycling applications. In the absence of any N-nitrosamine precursors, the destruction efficiency of N-nitrosamines was dependent on their molecular weight or the length of the alkyl chain in their molecular structure. Experiments conducted with RO concentrate showed that ozonation could lead to the formation of N-nitrosodimethylamine (NDMA) and N-nitrosodiethylamine (NDEA), resulting in an increase in concentrations of these N-nitrosamines. Nevertheless, ozonation was effective for destruction of N-nitrosamines with molecular weight greater than that of NDEA (102 g/mol).     

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.     

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.     

气相色谱—热能分析法测定啤酒中N—亚硝基二甲胺

本文采用硅藻土柱层析分离、气相色谱——热能分析法测定啤酒中N—亚硝基二甲胺的含量,并对方法的灵敏度、准确度及各种影响因素进行探讨。用于样品测定取得较为满意的结果。     

饮用水含氮消毒副产物NDMA分析技术研究进展

N-亚硝基二甲胺(NDMA)是强烈致癌物质--N-亚硝胺家族中的一员.近年来,研究发现饮用水氯化消毒之后会产生NDMA,引起了人们的广泛关注.本文简要介绍了消毒副产物NDMA的形成机理,阐述了NDMA样品预处理技术,包括:液液萃取(LLE)、固相萃取(SPE)和固相微萃取(SPME),并详述了气相色谱、气质联用、高效液相色谱和液质联用等分析方法,展望了今后的研究方向.     

Determination of attenuation rates of recycled water disinfection by‐products in a natural reservoir system using a laboratory‐based approach

A batch test approach was used to assess the in situ attenuation by natural reservoir systems of selected disinfection by‐products (DBPs). The aim was to determine which natural attenuation processes (volatilisation, photolysis and biodegradation) dominated for selected trihalomethanes (THMs) and N‐nitrosodimethylamine (NDMA), common DBPs present in reclaimed water which could be used to potentially augment drinking water supplies. Attenuation rates for THMs were found to be all very similar, with half‐lives ranging from 1.5–1.6 days for open batch tests. The dominant attenuation mechanisms for THMs were volatilisation with hydrolysis and biodegradation of potentially minor importance. NDMA had a half‐life of 3.5–4.3 days for vials exposed to light. The most important attenuation mechanism for NDMA was photolysis with volatilisation and biodegradation of minor importance. The results indicate that the selected DBPs could be effectively attenuated by a natural reservoir system such as a surface water reservoir.     

两种预氧化法与氯胺消毒联用对polyamlne形成NDMA的影响

预氧化处理与有机高分子絮凝剂联用会使含氮消毒副产物亚硝基二甲胺(NDMA)质量浓度上升,典型水处理工艺条件下NDMA的质量浓度为60～100 ng/L,为了解不同因素的影响及其反应机理,研究次氯酸钠氯化预氧化及高锰酸钾预氧化与聚环氧氯丙烷二甲胺(polyamine)在不同条件下联用并用氯胺消毒后NDMA的生成量.结果表明:随着预氧化剂投加量、pH、polyamine投加量及Br-质量浓度的增加,NDMA的生成量也相应增加;低质量浓度NH_4~+会导致NDMA生成量增加17. 5%左右,但随质量浓度增加,NDMA生成量逐渐减少至初始水平;随着NO_2~-质量浓度增加,NDMA生成量显著减少,当NO_2~-的质量浓度达到10 mg/L时,NDMA的生成量为最初的15%左右;氯化预氧化过程符合UDMH机理,而高锰酸钾预氧化过程包含UDMH机理及羟基自由基机理.     

壳聚糖及其衍生物对亚硝化反应的抑制作用

为了解壳聚糖及其衍生物对亚硝化反应的抑制作用,在体外模拟人胃液的条件下,用比色法及紫外光解法测定了壳聚糖及其衍生物对亚硝胺合成的阻断作用和对亚硝酸钠的清除作用。结果表明,壳聚糖及其衍生物对亚硝化反应均具有较强的抑制作用,对亚硝胺的阻断率达 52. 41% ~73 .20%,对亚硝酸钠的清除率达 50 .57%~73 .31%;在被测物中,脱乙酰度为 90%的壳聚糖在加入量为 6g/L时,对亚硝化反应的抑制作用最强。     

Chloramination of nitrogenous contaminants (pharmaceuticals and pesticides): NDMA and halogenated DBPs formation

Disinfection with chloramines is often used to reduce the production of regulated disinfection by-products (DBPs) such as trihalomethanes (THMs) and haloacetic acids (HAAs). However, chloramination can lead to the formation of N-nitrosamines, including N-nitrosodimethylamine (NDMA), a probable human carcinogen. Previous research used dimethylamine (DMA) as a model precursor of NDMA, but certain widely used tertiary dimethylamines (e.g. the pharmaceutical ranitidine) show much higher conversion rates to NDMA than DMA. This study investigates the NDMA formation potential of several tertiary amines including pharmaceuticals and herbicides. The reactivity of these molecules with monochloramine (NH₂Cl) is studied through the formation of NDMA, and other halogenated DBPs such as haloacetonitriles (HANs) and AOX (Adsorbable Organic Halides). Several compounds investigated formed NDMA in greater amounts than DMA, revealing the importance of structural characteristics of tertiary amines for NDMA formation. Among these compounds, the pharmaceutical ranitidine showed the highest molar conversion to NDMA. The pH and dissolved oxygen content of the solution were found to play a major role for the formation of NDMA from ranitidine. NDMA was formed in higher amounts at pH around pH 8 and a lower concentration of dissolved oxygen dramatically decreased NDMA yields. These findings seem to indicate that dichloramine (NHCl₂) is not the major oxidant involved in the formation of NDMA from ranitidine, results in contradiction with the reaction mechanisms proposed in the literature. Dissolved oxygen was also found to influence the formation of other oxygen-containing DBPs (i.e. trichloronitromethane and haloketones). The results of this study identify several anthropogenic precursors of NDMA, indicating that chloramination of waters impacted by these tertiary amines could lead to the formation of significant amounts of NDMA and other non-regulated DBPs of potential health concern (e.g. dichloroacetonitrile or trichloronitromethane). This could be of particular importance for the chloramination of wastewater effluents, especially during water reuse processes.     

UV/H_2O_2降解水中痕量NDMA的效能研究

采用UV/H2O2降解水中的痕量NDMA,考察了水中NDMA初始浓度、H2O2投量、pH、天然有机物及常见阴离子等因素的影响,并分析了NDMA的降解产物。结果表明,在UV辐照度为1 000μW/cm2、NDMA初始浓度为0.1 mmol/L、H2O2投量为20 mg/L、pH值为4的条件下,UV/H2O2对NDMA的降解效果较好(反应5 min后对NDMA的去除率接近100%);水中的天然有机物和Cl-、SO42-、NO3-、HCO3-等阴离子对NDMA的降解均有抑制作用,腐殖酸浓度越大其抑制作用越强,阴离子的抑制作用由大到小依次为HCO3-、NO3-、SO24-、Cl-;NDMA的主要降解产物为二甲胺和硝酸盐,此外还有少量亚硝酸盐、甲酸盐和甲胺生成。