PCDFs的Ah受体结合能力的定量结构效应关系

应用单苯环氯取代方法取G₁～G₁₀10个分子结构描述符,通过正向逐步线性回归方法构建对于Ah受体结合能力的定量结构-性质相关(QSAR)模型.与有关文献相比,此模型能更好地预测多氯代二苯并呋喃(PCDFs)竞争结合Ah受体logEC₅₀值,各自变量间不存在共线性.模型可以较好地反映PCDFs分子Ah受体结合能力与其分子氯取代位点之间的关系.     

3个城市生活垃圾焚烧炉飞灰中二噁英类分析

对3个城市生活垃圾焚烧炉飞灰中二英类浓度分布的实验研究表明,飞灰中二英类异构体的浓度分布具有相类似的特征,高氯代二英类的含量明显高于低氯代二英类.飞灰中二英类的毒性贡献主要来自多氯二苯并呋喃(PCDFs).布袋除尘器前添加活性炭粉末时,飞灰的二英类浓度比没有添加活性炭时高1.8倍,而尾气中二英类浓度相应降低.     

3个城市生活垃圾焚烧炉飞灰中二恶英类分析

对3个城市生活垃圾焚烧炉飞灰中二恶英类浓度分布的实验研究表明，飞灰中二恶英类异构体的浓度分布具有相类似的特征，高氯代二恶英类的含量明显高于低氯代二恶英类．飞灰中二恶英类的毒性贡献主要来自多氯二苯并呋喃(PCDFs)．布袋除尘器前添加活性炭粉末时，飞灰的二恶英类浓度比没有添加活性炭时高1．8倍，而尾气中二恶英类浓度相应降低。     

水中氯代苯酚的GC/MS分析

本文采用乙醚萃取地表水中氯代苯酚,利用气相色谱-质谱联用仪(GC/MS)定性定量分析水中2,4-二氯苯酚、2,4,6-三氯苯酚.探讨了萃取剂和pH值对萃取效率的影响.     

密度泛函方法预测二英类化合物(PCDD/Fs)的正辛醇/水分配系数

在B3LYP/6-31G水平上全优化计算了多氯代二苯并一对-二(噁)英和多氯代二苯并呋喃(PCDD/Fs)系列物的分子结构;基于得到的分子结构描述符,依据修正的线性溶解能理论,分别建立了PCDDs和PCDFs的正辛醇/水分配系数的定量结构-性质关系模型(R2分别为0.985和0.966),并用交叉验证法对模型进行了验证(q2分别为0.983和0.936),用t-检验对各变量进行了检验.检验结果表明,模型的预测能力优于AM1法、单苯环氯取代指数法和拓扑量子方法得出的模型.     

密度泛函方法预测二英类化合物(PCDD/Fs)的正辛醇/水分配系数

在B3LYP/6-31G水平上全优化计算了多氯代二苯并—对-二英和多氯代二苯并呋喃(PCDD/Fs)系列物的分子结构;基于得到的分子结构描述符,依据修正的线性溶解能理论,分别建立了PCDDs和PCDFs的正辛醇/水分配系数的定量结构-性质关系模型(R2分别为0.985和0.966),并用交叉验证法对模型进行了验证(q2分别为0.983和0.936),用t-检验对各变量进行了检验.检验结果表明,模型的预测能力优于AM1法、单苯环氯取代指数法和拓扑量子方法得出的模型.     

单苯环氯取代指数法预测二■英类化合物PCDFs的正辛醇/水分配系数

采用单苯环氯取代指数作为二恶英类化合物多氯代二苯并呋喃（PCDFs）的分子结构描述符，通过正向逐步线性回归方法建立了PCDFs的正辛醇／水分配系数（lgKow)与分子结构描述符之间的定量关系模型。与有关文献报道的模型相比，该模型不仅具有显著的相关性（n=51,Radj=0.871,SE=0.17334,在a=0.05时，F＝38．647，p0.000)，而且对于分子结构具有更好的区分能力，利用建立的模型，对没有lgKow文献值的其他85种PCDFs化合物给出了预测值。     

意大利的金枪鱼、箭鱼、鸬鹚以及家燕等体内的多氯萘、多氯联苯、多氯二苯-p-二恶英、多氯二苯并呋喃以及p,p''''-DDE

我们曾对从意大利收集的金枪鱼、箭鱼、普通鸬鹚以及家燕体内的p,p'-DDE、多氯联苯同类物(PCBs)、多氯二苯-p-二恶英(PCDDs)、多氯二苯并呋喃(PCDFs)以及多氯萘(PCNs)浓度进行过测量.     

超声波/零价铁体系降解五氯酚的机理

在超声波/零价铁体系中,以五氯酚为目标污染物,分别对各种形态铁离子浓度和羟基自由基表观生成率进行了定量测定,探讨了超声波与零价铁的协同作用机理.结果表明,在超声波/零价铁体系降解五氯酚过程中,同时存在超声波的羟基自由基氧化作用和零价铁的还原作用,其中超声波的羟基自由基氧化作用占主导,零价铁大大地促进了该体系羟基自由基的生成.同时,采用气相色谱.质谱联用仪测定中间产物,并结合相关研究推测,超声波/零价铁降解五氯酚主要是通过羟基自由基的氧化脱氯、五氯酚氧自由基的自身耦合,以及零价铁的还原脱氯3种降解途径完成的.     

垃圾焚烧与二■■

多氯二苯并-对-二■■(PCDDs)和多氯二苯并呋喃(PCDFs)是毒性极强的环境污染物质,垃圾焚烧又是大城市中引起二■■污染的主要来源。文中介绍了如何加强垃圾焚烧厂的运行管理,严格控制二■■的产生和排放等问题。      

Distribution characteristics and source identification of polychlorinated dibenzo-p-dioxin and dibenzofurans, and dioxin-like polychlorinated biphenyls in the waters from River Kanzaki, running through Osaka urban area, Japan

This is the first to elucidate the distribution and sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDFs),and dioxin-like polychlorinated biphenyls in the waters from Kanzaki River,which is one of the most heavily polluted rivers in Japan.The World Health Organization (WHO)-toxic equivalent quantities (TEQs) in waters from the mainstream exceeded the Japanese environmental standard (1.0 pg-TEQ/L).The PCDD/PCDFs were dominated by highly chlorinated DFs,which predominantly contributed to the WHO-TEQs,suggesting that the main causes would be the incineration-related wastes.To find the sources,the dioxin congener concentrations in water and sediment samples from its tributary small waterways were determined.Abnormally high WHO-TEQs were detected in a water (50 pg-TEQ/L) and a sediment sample (41,000 ng-TEQ/kg dry weight) near the industrial solid waste incinerators (ISWIs).The PCDD/PCDF characteristics agreed well with those of the incinerator-related wastes as seen in the mainstream.These facts indicate that the dioxin pollution in the mainstream could be largely related to the industrial wastes from the ISWIs.Here,a TEQ apportionment method was used to understand the contribution of the pyrogenic sources to the WHO-TEQs.The average contribution ratios of the pyrogenic sources to WHO-TEQs were more than 80% for river waters from the mainstream,indicating that the elevated WHO-TEQs in the mainstream had been largely caused by the ISWIs.     

Characteristics of air pollution by polychlorinated dibenzo-p-dioxins and dibenzofurans in the typical industrial areas of Tangshan City, China

The ambient air in vicinity of different industrial sources for PCDD/PCDFs was sampled by TSP/PM10 active samplers and passive PUF disk samplers in Tangshan City, a metropolis containing clusters of various industrial plants. The TEQ concentrations of PCDD/PCDFs ranged from 44.2 to 394.1 fg I-TEQ/m3 with an average of 169.9 fg I-TEQ/m3. 2,3,4,7,8-PeCDF was the dominant contributor to PTEQ, contributing 41% (12% to 55%), while 1,2,3,4,6,7,8-HpCDF, OCDD and OCDF were the major congeners for the total concentrations. The ratios of PPCDF/PPCDD reached 2.54 on average, suggesting that de novo synthesis in thermal processes played an important role to the airborne pollution of PCDD/PCDFs. The similarities congener profiles indicated that TSP and PM10 active sampling methods are comparable for the determination of the PCDD/PCDFs in ambient air, and the ratios of concentrations determined by the two methods suggested that the PCDD/PCDFs tended to stay in fine particles. It was found that 2,3,7,8-TCDF and OCDD were the dominating congeners in the passive PUF disks samples. Through principal components analysis, the coke industry was suggested to be a relatively high potential emission source for PCDD/PCDFs in the ambient air of Tangshan, which was possibly formed by de novo synthesis mechanism. In this study, the atmospheric impacts to the environment from di erent industrial sources could be ranked as follows (from high to low): coking, iron sintering, steel making, power generation and chlorinate alkali chemical production industries.     

气相色谱／质谱（GC／MS）联用在我国大气有机污染监测中的应用

概述ＧＣ／ＭＳ联用在我国大气有机污染监测中的应用，介绍大气中有机污染物，如多环芳烃、硝基多环芳烃、多氯二苯并二恶英、多氯二苯并呋喃、碳氢化合物、苯系物、恶臭、有机硫化合物、多组分有机污染物的测定。     

环境中二噁(口英)及其检测技术进展

从二(?)(?)类化合物的结构、来源、毒性等简要说明对其监测的必要性,且从仪器监测(包括气相色谱、气质联用、串联质谱等)和生物监测(包括利用指示生物、生物标志物等)概述了80年代以来国内外对二(?)(?)类物质尤其是几种极毒性化合物如多氯代二苯二(?)(?)(PCDDs)和多氯代二苯呋喃(PCDFs)等化合物的检测技术成果。     

两种典型生活垃圾焚烧炉烟气中二 相态分布特征

采集了机械炉排焚烧炉和循环流化床焚烧炉两种典型生活垃圾焚烧炉排放烟气样品,应用高分辨气相色谱/高分辨质谱(HRGC/HRMS)同位素内标稀释法分别测定了烟气不同相样品中17种2,3,7,8-位氯取代的PCDDs/PCDFs同类物的含量.结果表明,两种炉型中PCDDs/PCDFs同类物及毒性当量贡献率在冷凝水相中所占的比例均在85%以上,远远高于在滤筒相和XAD-2树脂相中所占的比例,机械炉排炉焚烧排放烟气中∑PCDFs与∑PCDDs的比值为0.77;而循环流化床焚烧排放烟气∑PCDFs与∑PCDDs的比值为5.28.机械炉排炉焚烧烟气三相中OCDD为优势分布,尤其是滤筒相中OCDD的百分比含量高达51.1%.流化床焚烧炉焚烧烟气滤筒、树脂、冷凝水相中没有出现某个单体对总浓度具有绝对优势的贡献.机械炉排焚烧炉和循环流化床焚烧炉排放的烟气中PCDFs的毒性当量贡献最大,尤其是单体2,3,4,7,8-PeCDF对总毒性当量的贡献均在30%以上.     

燃油式火化机排放烟气中二□英类污染水平和排放特征

对国内6台燃油式火化机排放烟气中的二□英类污染水平和排放特征进行了初步研究.结果表明:烟气样品中ρ(二□英类)为9.2～120.0 ng/m3〔273.15 K,101.325 kPa,φ(O₂)为11%换算值〕,毒性当量(TEQ)浓度为1.0～8.1 ng/m3;所有烟气样品中二□英类同类物分布相似,17种2,3,7,8-氯代二□英类同类物被全部检出,其中2,3,4,7,8-P₅CDF对毒性当量浓度的贡献最大;ρ(PCDFs)高于ρ(PCDDs),ρ(T₄CDFs)在PCDFs中最高;燃烧控制和烟气处理措施是影响燃油式火化机二□英类生成和排放的重要因素.      

两种典型生活垃圾焚烧炉烟气中二噁(口英)相态分布特征

采集了机械炉捧焚烧炉和循环流化床焚烧炉两种典型生活垃圾焚烧炉排放烟气样品,应用高分辨气相色谱/高分辨质谱(HRGC/HRMS)同位素内标稀释法分别测定了烟气不同相样品中17种2,3,7,8-位氯取代的PCDDs/PCDFs同类物的含量.结果表明,两种炉型中PCDDs/PCDFs同类物及毒性当量贡献率在冷凝水相中所占的比例均在85％以上,远远高于在滤筒相和XAD-2树脂相中所占的比例,机械炉排炉焚烧排放烟气中∑PCDFs与∑PCDDs的比值为0.77;而循环流化床焚烧排放烟气∑PCDFs与∑PCDDs的比值为5.28.机械炉排炉焚烧烟气三相中OCDD为优势分布,尤其是滤简相中OCDD的百分比含量高达51.1％.流化床焚烧炉焚烧烟气滤筒、树脂、冷凝水相中没有出现某个单体对总浓度具有绝对优势的贡献.机械炉排焚烧炉和循环流化床焚烧炉排放的烟气中PCDFs的毒性当量贡献最大,尤其是单体2,3,4,7,8-peCDF对总毒性当量的贡献均在30％以上.     

Effects of inorganic chlorine source on dioxin formation using fly ash from a fluidized bed incinerator

Chlorine source is indispensable for polychlorinated dibenzo-p-dioxin and furan (PCDD/F) formation during municipal solid waste (MSW) incineration. Inorganic chlorine compounds were employed in this study to investigate their effects on PCDD/F formation through heterogeneous synthesis on fly ash surfaces. A fly ash sample obtained from a fluidized bed incinerator was sieved to different size fractions which served as the PCDD/F formation sources. The capability of different metal chlorides which facilitate the formation of PCDDs/Fs was found to follow the trends: Na ＜ Mg ＜ K ＜ Al ＜ Ca, when two particle fractions of ＞177 μm and 104-125 μm were used in the experiments. However, the capability of NaCl, MgCl2 and KCl did not seem much different from each other, whereas CaCl2 and AlCl3 were much more active in PCDD/F formation. NaCl and MgCl2 were relatively effective to produce more PCDDs, while KCl, AlCl3 and CaCl2 generated more PCDFs during heterogeneous reactions occurring on fly ash. 2,3,7,8-TCDF was the most significant contributor to the toxicity of the PCDDs/Fs formed from inorganic chlorine sources. Decreasing the sizes of fly ash particles led to more active formation of PCDDs/Fs when NaCl was used as inorganic chlorine in the experiment. The highest PCDDs/Fs produced from particles with size ＜37 μm, while the lowest PCDDs/Fs produced from particles with size ＞177 μm. The toxicity generally increased with decreasing size of the fly ash particles. The formation of PCDDs was mainly facilitated by the two size fractions, 104-125 μm and ＜37 μm, while formation of PCDFs was favored by the two other size fractions, ＞177 μm and 53-104 μm.     

生活垃圾焚烧厂周边土壤中PCDD/Fs及重金属含量

为了解城市生活垃圾焚烧发电厂周边表层土壤中二噁英、重金属来源及分布特征,选取成都地区3座典型生活垃圾焚烧厂作为研究对象,开展了周边土壤中17种多氯二苯并对二噁英/呋喃（PCDD/Fs）及11种重金属含量监测.结果显示,土壤样品中的PCDD/Fs和重金属的浓度范围分别为0.25~7.5ng I-TEQ/kg和0.23～580.57mg/kg;3座垃圾焚烧厂周边土壤中多氯二苯并呋喃（PCDFs）的毒性当量浓度贡献率要高于多氯二苯并二噁英（PCDDs）,PCDFs毒性当量浓度平均贡献率达到55%;土壤样品中Cd、Hg、Pb、Cu、Zn之间具有良好的相关性,Hg、Pb、Zn与部分PCDFs具有良好的相关性,相关系数r分别为0.792、0.760、0.788,所对应的p值分别为0.034、0.047、0.035,并被归类为同一聚类,可将这部分重金属元素作为重金属示踪剂来表征PCDFs的来源.     

污泥中潜在的二■■污染物质

依据国内外最近的检测结果对污泥中二■■类物质的研究进行论述,探讨其来源、组成分布、环境行为及潜在危害。研究表明,焚烧过程排放?成了环境中二■■的本底来源,除此之外的二■■主要来源于废水处理(包括生活污水与工业污水)形成的污泥,并且污泥中二■■的含量较高。鉴于二■■的毒理特性、以往的二■■污染事件及我国对污泥的处理方式,急需查明堆肥与填埋处理的污泥中的二■■现状,并以此为依据制定二■■毒物的排放标准及其在环境中的限额。