Precursors and nitrogen origins of trichloronitromethane and dichloroacetonitrile during chlorination/chloramination

The formation of trichloronitromethane (TCNM) and dichloroacetonitrile (DCAN) was investigated during chlorination and chloramination of 31 organic nitrogen (org-N) compounds, including amino acids, amines, dipeptides, purines, pyrimidones and pyrroles. Tryptophan and alanine generated the greatest amount of TCNM during chlorination process and asparagine and tyrosine yielded the highest amount of TCNM during chloramination process. Tryptophan, tyrosine, asparagine, and alanine produced more DCAN than other org-N compounds regardless of chlorination or chloramination. TCNM and DCAN formation was higher by chlorination than by chloramination. NH₂Cl:org-N molar ratios, reaction time, and pH affected N-DBPs formation in varying degrees. TCNM and DCAN yields were usually high during chloramination of tyrosine, asparagine, and methylpyrrole under the following reaction conditions: NH₂Cl:org-N molar ratios greater than 10, reaction time for 1 d, and at pH 7.2. NH₂Cl as a major nitrogen origin in TCNM and DCAN was confirmed via labeled ¹⁵N-monochloramine during chloramination of tyrosine, asparagine and methylpyrrole. In contrast, the majority of nitrogen in TCNM originated from glycine, and that in DCAN originated from pyrrole. Based on the intermediates identified by gas chromatography/mass spectrometry (GC/MS), a pathway scheme was proposed for TCNM and DCAN formation.     

Effects of bromide and iodide ions on the formation of disinfection by-products during ozonation and subsequent chlorination of water containing biological source matters

This study aims to investigate the influence of the coexistence of halogen ions (bromide/iodide) and biological source matters on the speciation and yield of trihalomethanes (THMs), haloacetic acids (HAAs), and N-nitrosodimethylamine (NDMA) during the ozonation and subsequent chlorination of water. The results show that the concentrations of brominated THMs and iodinated THMs increased with increasing bromide and iodide concentration. These results may be attributed to the higher reactivity of hypobromous acid and hypoiodous acid generated from the ozonation and subsequent chlorination in the presence of bromide or iodide ions. The presence of bromide increased the species of brominated HAAs. There was a shift from chlorinated HAAs to brominated HAAs after increasing the concentration of bromide. The effect of iodide on HAA formation was more complex than bromide. For most samples, the concentration of total HAAs (T-HAAs) increased to the maximum and then decreased with increasing iodide concentration. The components of the organic precursors also significantly influenced the formation of brominated and iodinated disinfection by-products (Br-DBPs and I-DBPs). Humic acids produced more CHBr₃ (596.60 μg/L) than other organic materials. Microcystis aeruginosa cells produced the most tribromoacetic acid (TBAA, 84.16 μg/L). Furthermore, the yield of NDMA decreased with increasing bromide concentration, indicating that the formation of NDMA was inhibited by the high concentration of bromide.     

酪氨酸氯化过程中光谱变化特征及消毒副产物的生成规律

考察酪氨酸在不同投氯量条件下氯化后的余氯,紫外吸光度值和荧光光谱,以及消毒副产物对羟基苯乙腈(4-HBC)的生成特性。结果表明,随着投氯量的增加,余氯呈现先增加再减小再增加的趋势。在投氯量为0～0.5 mmolCl2/L时,增加投氯量可提高氯化后溶液的UV254、UV274和UV280值以及4-HBC的生成量,表明低投氯量时氯化可提高溶液中不饱和键的含量;而投氯量为0.5～1 mmol Cl2/L时,增加投氯量降低UV254、UV274和UV280值以及4-HBC的生成量,表明过量的氯亦可破坏溶液中的不饱和键。荧光光谱测试实验亦发现:在投氯量为0.05 mmol Cl2/L时,酪氨酸溶液氯化后的荧光峰强度明显增加,表明氯化可生成荧光强度较高的产物。过量的氯(0.5～1 mmol Cl2/L)则可破坏溶液中的荧光结构,降低荧光峰强度直至未检出。     

Effects of thiocyanate on the formation of free cyanide during chlorination and ultraviolet disinfection of publicly owned treatment works secondary effluent.

Cyanide has been detected in effluent of some publicly owned treatment works (POTWs) at levels exceeding influent concentration. Thiocyanate (SCN-) is a cyanide-related compound encountered in most POTW influents and may be decomposed to free cyanide (CN-) under some circumstances. Effects of SCN- on the formation of cyanide during chlorination and UV disinfection were studied through a laboratory study with synthetic solutions and POTW secondary effluent. Results indicated that CN- was detected in SCN- solutions after chlorination in which the chlorine dose or reaction time was not sufficient to destroy SCN-completely, thus ensuring no residual chlorine to destroy any CN-produced. It was also found that SCN can be broken down to yield cyanide by UV irradiation. In addition, SCN- was observed to cause significant positive error in the conventional total cyanide analysis technique involving acidic distillation and colorimetric measurement when nitrate was present in the sample.     

Effects of dissolved oxygen and iron aging on the reduction of trichloronitromethane, trichloracetonitrile, and trichloropropanone

Iron metal (Fe(0)) is a potent reductant capable of reducing a wide variety of halogenated organic compounds including disinfection byproducts (DBPs). These reduction reactions may play a role in DBP fate in iron water mains and potentially could be exploited to remove DBPs from drinking water or wastewater in a packed-bed configuration. Oxidants (i.e., dissolved oxygen (DO) and chlorine) present in the water, however, may decrease the DBP degradation rate by competing for reactive sites and rapidly aging or corroding the iron surface. Thus, batch experiments were performed to investigate the effect of DO on the degradation rates of selected DBPs by Fe(0). Experiments were performed under anaerobic conditions, in initially oxygen saturated buffer without DO control, and under controlled DO (approximately 4.0 or 8.0 mg l⁻¹) conditions. The effect of short-term (25–105 min) iron aging in DO-containing buffer on DBP degradation rate also was investigated in separate experiments. For fresh Fe(0), the degradation rates of trichloronitromethane (TCNM) and trichloroacetonitrile (TCAN) in initially oxygen saturated buffer were similar to their respective rates under anaerobic conditions. The degradation rate of 1,1,1-trichloropropanone (1,1,1-TCP), however, decreased significantly in the presence of DO and the effect was proportional to DO concentration in the controlled DO experiments. For a DO concentration of 4 mg l⁻¹, the degradation rate of the three DBPs was greater for longer aging times as compared to their respective rates after 25 min, suggesting the formation of a mineral phase that increased reactivity. For a DO concentration of 8 mg l⁻¹, the effects of increasing aging time were mixed. TCNM degradation rates were stable for all aging times and comparable to that under anaerobic conditions. The TCAN and 1,1,1-TCP degradation rates, however, tended to decrease with increasing aging time. These results suggest that the reduction of highly reactive DBPs by Fe(0) will not be affected by the presence of DO but that the reaction rates will be slowed by DO for DBPs with slower degradation kinetics.     

臭氧对饮用水中氯化消毒副产物生成的影响

以北京市某水厂砂滤池出水为实验原水,研究了臭氧曝气时间对实验原水中天然有机物（NOM）性质、结构及氯化消毒副产物生成的影响。通过高效凝胶色谱、三维荧光光谱、红外光谱等检测分析方法对水中NOM进行表征后发现,经臭氧作用后水样DOC浓度升高、亲水性增加、芳香性及重均分子量下降。有机物中羟基、碳碳双键或碳氮双键及其共轭体系、脱质子羧基官能团与氯反应活性较强。综合考虑臭氧作用后NOM性质、结构变化及氯化消毒副产物生成量的改变,选择最佳臭氧接触时间为12 min。     

陶瓷烧成中气氛及温度对NOX生成的影响

通过对不同烧成气氛NOX的生成进行测试分析,得出还原气氛可抑制NOX的生成.但在没有催化剂存在的情况下,CO对NO的还原效果不显著;其次,在烧成温度较低(1 200 ℃以下)、高温阶段温度场均匀性较好且使用洁净燃料(即含氮量较小的燃料)的情况下,快速升温将导致NOX生成的增加,此时快速型NOX起主要作用;第三,烧嘴的合理布置、改善窑体结构和加强高温阶段窑内温度场的均匀性可以减少NOX的生成.     

The formation of chlorodibenzo-p-dioxins by air oxidation and chlorination of bituminous coal

A well characterized bituminous coal was subjected to high temperature air oxidation and chlorination. After an extensive cleanup procedure, the reaction products were analyzed for chlorinated dibenzo-p-dioxins by gas chromatography-mass spectrometry. Substantial quantities of chlorodibenzo-p-dioxins, some of which are known to be highly toxic, were observed with chlorination by hydrogen chloride and chlorine gas.     

Relationship between chlorine consumption and chlorination by-products formation for model compounds

The objective of this research is to investigate the relationship between chlorine decay and the formations of disinfection by-products (DBP), including trichloromethane (TCM) and chloroacetic acid (CAA) in the presence of four model compounds, i.e., resorcinol, phloroglucinol, p-hydroxybenzoic acid, and m-hydroxybenzoic acid. The chlorine degradation in model compounds with OH and/or COOH functional groups were rapid after chlorination. The TCM yields of carboxylic group substituted compounds (3-hydroxybenzoic acid [3-HBA], 4-hydroxybenzoic acid [4-HBA]) were found to be lower than that of the m-dihydroxy substituted compounds. Phloroglucinol, with one more OH substitution group than resorcinol, tends to form significant amounts of CAA after chlorination. However, it was observed that with the COOH substitution of 3-HBA and 4-HBA tend to exhibit more CAA formation potential than resorcinol. The developed parallel second and first-order reaction model for chlorine demand has been successfully utilized for TCM, CAA and DBP formation modeling. A high correlation between CAA and TCM was observed for the model compounds.     

饮用水中含氮消毒副产物卤代腈(氰)的生成特性与控制研究进展

卤代腈(氰)是水处理过程中产生的一类含氮的氯化消毒副产物。鉴于这种物质有极强的致畸和致突变性,其细胞毒性也远大于三卤甲烷和卤乙酸等常规消毒副产物,因此成为近年来饮用水中颇受关注的含氮消毒副产物种类之一。卤代腈(氰)在水厂出厂水中被大量检出,其质量浓度基本维持在μg/L,而采用氯胺消毒的出厂水中其浓度明显高于自由氯消毒方式。重点对卤代腈(氰)的物质种类、理化特性、遗传毒性、生产机制、检测方法及控制方法进行综述。鉴于多数卤代腈(氰)类消毒副产物均具有含量低、亲水性强等特点,若生成将难以在饮用水处理工艺中有效去除,因此如何有效控制其生成是卤代腈(氰)研究的主要发展方向。     

Effects of chlorination on the adhesion strength and deflocculation of activated sludge flocs.

A side effect of the application of chlorine for controlling filamentous bulking is deflocculation of floc-forming bacteria, which may cause unacceptable effluent deterioration depending on dosing. It was assumed that chlorine may adversely affect the adhesion ability of floc bacteria, promoting their erosion in shear flow. The effect of chlorination on the strength of activated sludge flocs was investigated. The adhesion-erosion (AE) model developed by Mikkelsen and Keiding was used to interpret results from deflocculation tests with varying shear and solids concentration. The AE model yields the adhesion enthalpy (deltaHG/R) of cells in sludge flocs and parameters from the model were used to quantify the sludge in terms of floc strength. Two activated sludges with different initial characteristics were studied. The resulting model parameters showed that the AE model was suitable for quantifying the bond energy of particles to the activated sludge exposed to chlorine. For one activated sludge, adhesion of cells was largely unaffected by the applied chlorine doses. A second sludge showed reduced adhesion strength with chlorine, leading to increasing deflocculation. The simple batch test and AE model proved valuable for assessing the effect of chlorination on the flocs in activated sludge. By use of these procedures, it is possible to determine acceptable chlorine dosing to avoid excessive deflocculation and effluent deterioration.     

Modeling the formation of chlorination by-products in river waters with different quality

Water chlorination results in formation of a variety of organic compounds, known as chlorination by-products (CBPs), mainly trihalomethanes (THMs) and haloacetic acids (HAAs). Factors affecting their concentrations have been found to be organic matter content of water, pH, temperature, chlorine dose, contact time and bromide concentration, but the mechanisms of their formation are still under investigation. Within this scope, chlorination experiments have been conducted with river waters from Lesvos island, Greece, with different water quality regarding bromide concentration and organic matter content. The factors studied were pH, time and chlorine dose. The determination of CBPs was carried out by gas chromatography techniques. Statistical analysis of the results was focused on the development of multiple regression models for predicting the concentrations of total trihalomethanes and total HAAs based on the use of pH, reaction time and chlorine dose. The developed models, although providing satisfactory estimations of the concentrations of the CBPs, showed lower correlation coefficients than the multiple regression models developed for THMs only during previous study. It seems that the different water quality characteristics of the two river waters in the present study is responsible for this phenomenon. The results indicate that under these conditions the formation of THMs and HAAs in water has a more stochastic character, which is difficult to be described by the conventional regression techniques.     

pH对预氧化沸石滤柱启动过程中除锰效率的影响

针对当前接触氧化除锰法启动期较长的问题,采用改性沸石滤料耦合次氯酸钠预氧化辅助滤柱启动,采用扫描电子显微镜(SEM)、能量色散 X 射线光谱(EDS)、X射线衍射(XRD)、X 射线光电子能谱(XPS)对滤料进行分析,探究了原水pH对滤柱启动中锰去除效率的影响,并对持续运行过程中次氯酸钠的投加量进行了优化,对改性沸石滤料进行静态吸附实验,并在进水pH分别为6.5、7.0、7.5时进行滤柱启动实验。结果表明,改性沸石滤料对Mn²⁺的吸附符合Langmuir模型与准二级动力学方程,当pH为5.5~8.0时,随pH升高改性沸石滤料对Mn²⁺的去除率上升。在3种pH条件下,滤柱的锰穿透期分别为5、8 和9 d,并分别在第20、16和14天启动成功;次氯酸钠预氧化启动的3种滤柱次氯酸钠最低投加量分别为0.8、0.3与0.2 mg·L⁻¹。SEM与XRD表征结果证实了水钠锰矿在滤料表面的出现;而EDS与XPS结果分别表明,更高的pH会同时带来滤料表面锰元素含量和锰价态的升高。以上研究结果可为地表水水厂中对除锰有利的pH范围及沸石在启动过程中对锰的吸附作用提供参考。     

Formation of volatile halogenated by-products during chlorination of isoproturon aqueous solutions

The present paper deals with the formation of volatile halogenated by-products (POX) during the chlorination (160 mg/l) of aqueous solutions of the herbicide isoproturon (40 mg/l). Chlorination reactions have been carried out over 48 h, at ambient temperature, at two pHs (6 and 9) and in the presence or not of bromide ions (80 mg/l). The main results obtained have been as follows: (1) in the presence of bromide, isoproturon degradation is rather fast and it results affected by pH, complete isoproturon degradation is achieved within 1 and 15 min at pH 6 and 9, respectively; (2) in the absence of bromide herbicide degradation is slow (complete degradation is achieved within 180 min) and it is not affected by pH; (3) at pH 6, regardless of the presence of bromide, the maximum amount of POX formed is low (approximately 15 micromol X-/l) and remains constant during the reaction; (4) at pH 9 the amount of POX formed is far greater and continuously increases during the reaction, reaching a value of about 110 micromol X-/l after 48 h; (5) two different groups of by-products have been identified by solid phase micro extraction (SPME)-gas chromatography (GC)-mass spectrometry (MS) for the reactions carried out with or without bromide; among them, aliphatic as well as aromatic by-products containing chlorine, bromine or both halogens are present even though the most abundant are halogenated-methane derivatives (haloforms); pH value affects the amount of these by-products but does not modify their chemical nature.     

温度和表面活性剂对菲在土壤中吸附的影响

通过静态吸附实验,研究了北京地区土壤对菲的吸附行为,考察了温度和表面活性剂对菲吸附的影响.结果表明,6种土样对菲的吸附等温线均较好地符合Freundlich吸附模式,其吸附能力的大小顺序为:轻壤土>轻粘土>砂壤土>中壤土>重壤土>紧砂土;温度升高不利于菲在土壤中的吸附;十二烷基苯磺酸钠(LAS)和十六烷基三甲基澳化铵(CTAB)均利于菲在土壤表面的解吸,LAS和CTAB对菲的解吸率最高可达66.2%和31.8%,且LAS的解吸效果更好.     

Factors on the formation of disinfection by-products MX, DCA and TCA by chlorination of fulvic acid from lake sediments

[3-Chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone] (MX) and chlorinated acetic acids such as dichlorinated acetic acid (DCA) and trichlorinated acetic acid (TCA) have always been the focus of disinfection by-products (DBPs) studies. In order to find out the influences of reaction time, TOC, chlorine dose, pH and temperature on the formation of MX, DCA and TCA, we extracted fulvic acid (FA) from the sediment of Tai Lake, and conducted simulated chlorination of samples rich in FA. Results showed positive relationship between TOC and the yields of MX, DCA and TCA. But the influences of pH, chlorine dose, reaction time, and temperature are quite complex. The optimal chlorination condition for the formation of MX is pH = 2, T = 45 degrees C, C/Cl2 = 1/4, t = 12 h. Lower pH, longer time, greater chlorine dose can result in greater yield of both DCA and TCA, and there is a strong linear relationship between the formation of DCA and TCA.     

芳香类有机物氯化生成消毒副产物的特性研究

选择有代表性的芳香类有机物,在含有腐殖酸的水溶液中进行氯化试验.测定三卤甲烷和卤乙酸的生成特性.并分析有机物的化学结构对生成消毒副产物的影响.结果表明.各受试物氯化生成消毒副产物的活性和反应速率排序为间苯二酚>对苯二酚>邻苯二酚>苯酚>苯胺>苯甲酸>硝基苯;芳香类有机物苯环上官能团的性质、数量和位置等影响消毒副产物的生成;间苯二酚的氯化反应可分为快速反应阶段和慢速反应阶段.     

Effects of regional differences in waste composition on the thermal formation of polychlorinated aromatics during incineration

Two artificial wastes (A and B) whose contents reflect regional differences in municipal solid waste composition, were used to investigate the thermal formation of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and naphthalenes (PCNs) during incineration. Flue gas samples were simultaneously collected at three ports in the post-combustion zone corresponding to flue gas temperatures of 400, 300, and 200 °C. The combustion of Waste B, which had a higher chlorine and metal content than Waste A, produced greater levels of highly-chlorinated homologues, as demonstrated by a higher degree of chlorination. The total concentrations of PCDDs, PCDFs, PCBs, and PCNs formed in the combustion of both wastes increased as temperature decreased along the convector. There were no significant differences in total concentrations between Waste A and Waste B combustion at specific temperatures, with exception of PCDFs at 400 °C. Orthogonal Projections to Latent Structures Discriminant Analysis (OPLS-DA) modeling, used to evaluate the data for all compound groups, suggest that during flue gas quenching at temperatures of 400 °C low-chlorinated homologues are preferentially formed in the presence of copper, which is known to be a very active catalyst for this process. At 300 and 200 °C, the formation of highly-chlorinated homologues is favored.