Factors influencing the photodegradation of N -nitrosodimethylamine in drinking water

In order to provide basic data for practical application, photodegradation experiment of N-nitrosodimethylamine (NDMA) in aqueous solution was carried out with a low-pressure Hg lamp. Effects of the initial concentration of NDMA, solution pH, dissolved oxygen, and the presence of humic acid on NDMA photodegradation were investigated. NDMA at various initial concentrations selected in this study was almost completely photodegraded by UV irradiation within 20 min, except that at 1.07 mmol/L, NDMA could be photodegraded almost completely in the acidic and neutral solutions, while the removal efficiency decreased remarkably in the alkaline solution. Dissolved oxygen enhanced the NDMA photodegradation, and the presence of humic acid inhibited the degradation of NDMA. Depending on the initial concentration of NDMA, NDMA photodegradation by UV obeyed the pseudo-first-order kinetics. Dimethylamine, nitrite, and nitrate were detected as the photodegradation products of NDMA. ¹O₂ was found to be the reactive oxygen species present in the NDMA photodegradation process by UV, based on the inhibiting experiments using tert-butanol and sodium azide.     

The chlorination transformation characteristics of benzophenone-4 in the presence of iodide ions

Benzophenone-type UV filters are a group of compounds widely used to protect human skin from damage of UV irradiation. Benzophenone-4 (BP-4) was targeted to explore its transformation behaviors during chlorination disinfection treatment in the presence of iodide ions. With the help of ultra performance liquid phase chromatograph and high-resolution quadrupole time-of-flight mass spectrometer, totally fifteen halogenated products were identified, and five out of them were iodinated products. The transformation mechanisms of BP-4 involved electrophilic substitution generating mono- or di-halogenated products, which would be oxidized into esters and further hydrolyzed into phenolic derivatives. The desulfonation and decarboxylation were observed in chlorination system either. Obeying the transformation pathways, five iodinated products formed. The pH conditions of chlorination system determined the reaction types of transformation and corresponding species of products. The more important was that, the acute toxicity had significant increase after chlorination treatment on BP-4, especially in the presence of iodide ions. When the chlorination treatment was performed on ambient water spiked with BP-4 and iodide ions, iodinated by-products could be detected.     

水中萘普生的紫外光降解机制及其产物毒性研究

以120 W汞灯为紫外光光源,通过活性氧物种(ROS)的淬灭实验和溶解氧(DO)浓度实验和发光菌毒性实验,对水中萘普生(NPX)的降解机制、反应动力学及其产物毒性进行了研究.结果表明,NPX的紫外光降解过程包括了直接光解和ROS参与的自敏化光解两个过程,同时.OH、1O2、O.2-的自敏化光解贡献率分别为0.1%、80.2%、35.7%;溶解氧浓度实验表明,溶解氧对萘普生的降解具有抑制作用,而且浓度越大,抑制效果越明显;发光菌毒性实验表明,萘普生光降解生成了具有较萘普生更高风险的中间产物.本研究中萘普生的所有光解实验过程均符合准一级动力学方程.     

几种酰胺类除草剂的光降解及其致突变性

对３种常见的酰胺类除草剂乙胺,异丙甲草胺,丁草胺的光降解进行了研究,采用Ａｍｅｓ试验方法对母体和光降解产物的致突变性进行了检验,结果表明,在紫外灯照射下,这３种除草剂的光降解均较符合一级动力学,其降解速率次序为：异丙草胺〉乙草胺〉丁草胺。     

除草剂乙草胺、异丙甲草胺的光降解及其致突变性

对两种常见的酰胺类除草剂乙草胺、异丙甲草胺的光降解进行了研究,采用Ames试验方法对母体及其光降解产物的致突变性进行了检验．结果表明,初始ｐＨ值的变化对这两种除草剂的光降解速率无明显影响,异丙甲草胺比乙草胺更易于发生光降解．乙草胺在光降解前后均表现出无致突变性;异丙甲草胺本身具有致突变性,在光降解过程中未表现出有其它致突变性物质产生．     

腐殖酸光敏化降解土壤中多环芳烃的动力学

多环芳烃化合物(PAHs)由于致癌、致畸和致突变而受到广泛关注。实验以多环芳烃菲(Phe)和芘(Pyr)为目标污染物,研究了腐植酸和紫外辐射强度对PAHs光降解动力学的影响,及腐植酸光敏化光降解土壤中PAHs的机制.结果表明,腐殖酸光敏化降解Phe和Pyr符合一级动力方程,随着腐殖酸投加量的增加,Phe和Pyr的动力学常数也逐渐增加,半衰期缩短,在添加0、10、20、30、40 mg/kg腐植酸后,Phe的半衰期分别为52.90、47.79、43.86、37.87、34.48 h,Pyr的半衰期分别为45.90、38.50、36.09、30.26、29.74 h;腐殖酸可以将吸收光能传递给土壤中Phe和Pyr使其发生敏化光解,也可以使Phe和Pyr发生光氧化反应;随着辐射强度的增加,PAH光降解速率增加。该研究为应用腐殖酸光敏化降解土壤中PAHs有机污染物提供了参考依据。     

丁苯橡胶生产废水的生物降解特性

为研究丁苯橡胶生产废水的好氧生物降解特性,对某石化企业丁苯橡胶生产装置的生产废水进行好氧处理,并采用液液萃取-气相色谱/质谱、三维荧光光谱、紫外吸收光谱等手段对水质指标进行表征. 结果表明:经好氧生物降解后,丁苯橡胶废水中ρ(COD_Cr)和ρ(DOC)分别降至155和76 mg/L,COD_Cr和DOC去除率分别为76.07%和70.08%;废水中二苄胺、苯乙烯和十二烷基二甲基叔胺等9种主要特征有机物19 d内可被完全降解. 丁苯橡胶生产废水在λ_Ex/λ_Em(激发波长/发射波长)为225 nm/340 nm、215 nm/290 nm,275 nm/340 nm处有3个荧光峰,分别由二苄胺、十二烷基二甲基叔胺、苯乙烯、甲苯和苯甲醛等胺类、苯乙烯和芳香族化合物等有机物产生,好氧生物降解能去除废水中的绝大部分荧光物质,荧光峰强度的总去除率达到93.87%;废水中二苄胺、十二烷基二甲基叔胺、4-甲基环己酮、苯甲醛,苯乙烯、甲苯等有机物使丁苯橡胶生产废水分别在波长190~230、230~250、250~400 nm处有紫外吸收,好氧生物降解对UV₂₅₄的去除率达到52%. 研究显示,丁苯橡胶废水经单独好氧生物处理不能达到GB 31572—2015《合成树脂工业污染物排放标准》的要求,需结合其他方式进行联合处理.      

Photodegradation of perfluorooctanoic acid by 185 nm vacuum ultraviolet light

The photodegradation of persistent and bioaccumulative perftuorooctanoic acid （PFOA） in water by 185 nm vacuum ultraviolet （VUV） light was examined to develop an effective technology to deal with PFOA pollution. PFOA degraded very slowly under irradiation of 254 nm UV light. However, 61.7% of initial PFOA was degraded by 185 nm VUV light within 2 h, and defluorination ratio reached 17.1%. Pseudo first-order-kinetics well simulated its degradation and defluorination. Besides, fluoride ion formed in water, 4 shorter-chain perfluorinated carboxylic acids （PFCAs）, that is, perfluoroheptanoic acid, perfluorohexanoic acid, perfluoropentanoic acid, and perfluorobutanoic acid. These were identified as intermediates by LC-MS measurement. These PFCAs consecutively formed and further degraded with irradiation time. According to the mass balance calculation, no other byproducts were formed. It was proposed that PFCAs initially are decarboxylated by 185 nm light, and the radical thus formed reacts with water to form shorter-chain PFCA with one less CF2 unit.     

Formation pathways of brominated products from benzophenone-4 chlorination in the presence of bromide ions

The brominated products, formed in chlorination treatment of benzophenone-4 in the presence of bromide ions, were identified, and the formation pathways were proposed.Under disinfection conditions, benzophenone-4 would undertake electrophilic substitution generating mono- or di-halogenated products, which would be oxidized to esters and further hydrolyzed to phenol derivatives. The generated catechol intermediate would be transformed into furan-like heterocyclic product. The product species were p H-dependent,while benzophenone-4 elimination was chlorine dose-dependent. When the chlorination treatment was performed on ambient water spiked with benzophenone-4 and bromide ions, most of brominated byproducts could be detected, and the acute toxicity significantly increased as well.     

水体中几种无机离子对硝酸根敏化甲芬那酸光降解影响研究

以中压汞灯为光源,研究环境浓度范围内硝酸根对甲芬那酸(MEF)光降解的影响机制.结果表明,甲芬那酸在不同浓度硝酸根溶液中的光解反应符合准一级动力学规律,其降解速率常数随硝酸根离子浓度增大而增大,当硝酸根离子浓度由0增至1 mmol·L-1时其速率常数由0.00627 min-1增至0.0232 min-1;以异丙醇为分子探针检测到羟基自由基存在于MEF光解过程中;光解过程中产生亚硝酸根,其浓度随着反应的进行而不断增大;碱性水环境对硝酸根敏化甲芬那酸的光解反应有利;碳酸盐、氯离子、三价铁对硝酸根敏化甲芬那酸光解产生抑制作用.采用UPLC/MS/MS对硝酸根敏化MEF光降解产物进行鉴定,并提出3条可能的光解路径.毒性研究表明,在硝酸根敏化甲芬那酸光降解过程中,生成了具有较甲芬那酸而言更高风险的中间产物.     

DGB处理二级出水用于地下回灌的风险评价

以北京高碑店二级出水为对象,进行了二级出水地下回灌的DGB深度处理工艺的风险评价.GC/MS探测到的优先污染物四氯化碳引起的致癌风险小,可以忽略.二级出水经深度处理,除Cd,Cr略高于回灌标准,其余重金属含量低于回灌要求;通过加氯消毒,可满足回灌水卫生要求.DGB和土壤含水层处理工艺可去除部分致突物,残余的主要是移码型氯化致突物,它们有较强的致突性.      

焦化废水中有机物在A1-A2-O系统各段的降解与转化

在厌氧酸化－缺氧－好氧（A1－A2－O）生物膜系统小试装置中处理焦化废水，以探讨有机物在各阶段的降解与转化情况。通过UV吸收光谱及GC／MS分析发现，上海焦化厂废水中的有机组分主要为：甲酚、苯酚、二甲酚等酚类化合物，及以喹啉、吲哚为代表的含氮杂环化合物，约占有机物总量的90％。经A1－A2－O生物膜系统处理后，大部分有毒有害难降解有机物得到了降解和转化。厌氧段中原有物质浓度的增加和新物质的生成，是厌氧酸化使部分有机物降解产生中间产物而造成；缺氧段使大部分有机物被完全降解或转化，还产生一些新的简单有机物，如卤代烃、酯类、醛类等；经好氧段反应后，有机物进一步降解和转化，部分被完全去除，在降解转化过程中又产生了一些中间产物和衍生物，如苯酚、羟基喹啉等。     

黄浦江上游水源保护区工业废水的致突变性

对黄浦江上游水源保护区9家工厂工业废水应用Ames试验进行致突变性研究,结果表明,这些废水对TA_(98)菌株均有明显的致突变作用,其中有2家厂的废水未经活化对TA_(100)有致突变作用。通过计算最低致突变剂量和致突变指数,确认了排放大户,为有效地控制排放提供依据。     

Acute toxicity formation potential of benzophenone-type UV filters in chlorination disinfection process

Benzophenones （BPs） are a class of widely used UV filters, which have been frequently detected within multiple environmental matrices. Disinfection is a necessary process in water treatment processes. The transformation behaviors and toxicity changes of 14 BP-type UV filters during chlorination disinfection treatment were investigated in this study. A new index, the acute toxicity formation potential, was proposed to evaluate the toxicity changes and potential risks of BP-type UV filters during chlorination treatment. It was found that 13 of 14 BP-type UV filters exhibited toxicity decreases in the chlorination disinfection process, more or less, while one showed a toxicity increase. The toxicity changes were dependent on substitution effects, such that 2,4-di-hydroxylated or 3-hydroxylated BPs exhibited significant toxicity decreases after chlorination treatment due to the ready cleavage of the aromatic ring. Importantly, the acute toxicity changes could be duplicated in an ambient water matrix.     

邻苯二甲酸酯的光降解研究

为了了解水环境中邻苯二甲酸酯(PAEs)的降解及归趋,对紫外光照射下邻苯二甲酸二甲酯(DMP),邻苯二甲酸二乙酯(DEP)和邻苯二甲酸二丁酯(DBP)的光降解过程进行了研究,并采用气相色谱-质谱联用技术分别对3种物质降解过程中生成的中间体进行了分析,提出了可能的降解机理.研究结果显示,所测试的3种邻苯二甲酸酯的降解过程均符合一级反应动力学.以UV/H2O2工艺降解DMP,浓度为10.0mg·L-1的DMP在H2O2为20.0 mg·L-1条件下,光照45min降解率可达90%以上.对邻苯二甲酸酯及H2O2的初始浓度、光照时间及pH值等因素对降解过程的影响进行了研究,以期为该方法的实际应用提供必要的基础.     

几种消毒剂对饮水致突变活性的影响

本研究应用Ａｍｅｓ致突变试验对武汉东湖水分别经氯、二氧化氯和臭氧消毒处理后的致突变活性进行了检测与比较。结果表明：东湖水以及臭氧消毒处理水样未呈现致突变性,氯与二氧化氯处理的水样致突变性检测结果为阳性,这３种消毒剂处理的各水样致突变比活性强度顺序由强至弱依次为氯〉二氧化氯〉臭氧;同时对东湖水用高锰酸钾预处理,以降低氯化消毒饮水致突变活性的效果也进行了比较,结果发现用高锰酸钾预处理东湖水,可降低氯化     

异丙草胺光解体系中溶解氧的增强效应

研究了异丙草胺光解过程中溶解氧的协同效应,在不同初始浓度溶解氧存在时异丙草胺在水中的光解规律.随着溶解氧初始浓度的增加,光解速率和效率均有提高,其中最高和最低光解效率相差30%.初始溶解氧浓度达到7.5mg/L后,光解速率和效率出现了平台效应,并且随着溶解氧浓度增加而有所下降.伴随异丙草胺的光解,溶解氧也有消耗,可以推测溶解氧也参与了光反应.通过对降解产物的分析,发现含高浓度溶解氧和缺氧条件下的光解产物基本一致,但部分光解产物生成量不同.通过光解体系做自旋捕捉实验,推测可能是通过单线态氧¹O₂机制进行光氧化.     

碱减量印染废水特征污染物的生物降解特性

利用气相色谱-质谱联用(GC/MS)和液相色谱-质谱联用(LC/MS)对碱减量印染废水特征污染物在不同条件下生物降解产物进行了研究.结果表明,对苯二甲酸(TA)、分散橙4RL、分散蓝2BLN3种特征污染物在好氧环境和厌氧环境中都可以降解,其中TA最容易降解,2BLN次之,4RL的生物降解性能最差.4RL分解过程产生大量对微生物具有很强的抑制作用的苯胺类物质;易降解物质的添加可以增强难降解物质的分解,这种作用在厌氧条件下更加明显.对特征污染物的分解规律进行了分析和推断.     

光催化降解有机磷农药的研究

研究以ＴｉＯ２粉末作为光催化剂,光降解３种不同结构的有机磷农药的可行性。结果表明,有机磷农药结构不同其光降解率不同;浓度１．０×１０－４ｍｏｌ／Ｌ的４种有机磷农药,３７５Ｗ中压汞灯照射４０ｍｉｎ有机磷将完全转变为无机磷,并检测出人效磷农药催化降解的部分中间产物。研究光催化剂ＴｉＯ２的用量、空气流量、外加Ｆｅ３＋浓度对光催化降解的影响,并初步探讨了机理。     

Photodegradation of acetochlor in water and UV photoproducts identified by mass spectrometry

The sunlight photodegradation half-lives of 20 mg/L acetochlor were 151, 154 and 169 days in de-ionized water, river water and paddy water, respectively. When exposed to ultraviolet (UV) light, acetochlor in aqueous solution was rapidly degraded. The half-lives were7.1, 10.1, and 11.5 min in de-ionized water, river water and paddy water, respectively. Photopreduets of acetochlor were identified by gas chromatography/mass spectrometry(GC/MS) and found at least twelve photoproducts resulted from dechlorination with subsequent hydrtrxylation and cyclization processes. The chemical structures of ten photoproducts were presumed on the basis of mass spectrum interpretation and literature data. Photoproducts are identified as 2-ethyl-6-methylaniline; N, N-diethylaniline ; 4, 8-dimethyl-2-oxo- 1,2,3,4- tetrahydroquino-line; 2-oxo-N-(2-ethyl-6-methylphenyl)-N-(ethoxymethyl) acetamide; N-(ethoxymethyl)-2‘-ethyl-6‘-methylformanilide; 1-hydroxyaeetyl-2-ethoxyl-7-ethylind ole; 8-ethyl-l-ethoxymethyl-2-oxo-1, 2, 3, 4-tetrahydroquinoline; 4, 8-dimethyl-l-ethoxymethyl-2-oxo-1, 2, 3, 4-tetrahydroquinoline; 2-hydroxy-2‘-ethyl-6‘-methyl-N-(ethoxymethyl) acetanilide and a compound related to acetochlor. The other two photoproducts were detected by GC/MS although their chemical structure was unknown.