The effect of inorganic and organic chlorine on formation of highly chlorinated organic compounds during incineration: Laboratory pilot study

Aliphatic liquid as a basic fuel was incinerated in a laboratory scale pilot plant. Inorganic chlorine and organic chlorine mixed with basic fuel were used as additive chemicals. Sodium chloride (NaCl) and tetrachloroethylene (C₂Cl₄) were used as the sources of inorganic and organic chlorine. Combustion parameters were adjusted for optimum combustion and, consequently, the amount of particles in flue gases was low. The concentrations of chlorine in flue gases were high enough for possible formation reactions of organic chlorinated compounds in all of the chlorine input tests. An increase in chlorine input did not significantly increase the amounts of highly chlorinated organic compounds, like PCDD/Fs. The main result was that chlorophenol concentrations increased in parallel with organic chlorine input. Comparing organic chlorine to inorganic chlorine tests showed that more highly substituted PCDD/F congeners were formed when organic chlorine was the additive chlorine source. The formation of highly chlorinated organic compounds such as PCDD/Fs requires not only chlorine and aliphatic fuel to be formed, but some catalysts are also needed.     

PCDD/F in waste water discharges from flue gas scrubbers of waste incinerators and coal operated power plants

Scrubber water samples from different combustion plants and gypsum samples as obtained in the flue gas washing with lime water were analyzed for PCDD/F. Three of the investigated nine scrubber water samples showed PCDD/F contents between 0,4 and 11,5 ng I-TEq/1 where as in the 17 gypsum samples examined only in a few cases very low levels of HpCDD and OCDD could be detected.     

Survey of dioxin sources in the Baltic Region (extended summary)

The present paper summarises the results of the project: 'Survey of Anthropogenic Sources of Dioxins and Furans in the Baltic Region'. As a part of the project, inventories have been carried out in Estonia, Latvia, Lithuania and Poland by applying the toolkit for quantification of dioxin and furan releases developed by UNEP Chemicals. The main route of direct releases to the environment is emission to air. Total emission to air from Poland was estimated at 490 (88-1,300) g I-TEQ/year, whereas the emissions from Estonia, Latvia and Lithuania were estimated as being 14 (2.4-54), 23 (2.6-63) and 17 (2.6-38) g I-TEQ, respectively. In general, the uncertainty on the estimates is very high, and recommendations regarding further development of the inventories have been made, and measures for reducing the releases have been provided.     

氯代二恶英微生物降解性的初步探讨

本研究通过分离和筛选，从氯苯生产车间附近土壤和施用五氯酚除草剂的湖泊底泥中选出八支菌株，均能降解一氯代二恶英，３周内最多可降解４５％，但随氯取代数的增加而降解能力减弱，多数菌株不能降解三氯代二恶英，选择邻二氯苯为共代谢物的初级营养物，４１号株３周内可降解３３％三氯代苯基二恶英，说明选择适当的共代谢物，可改善微生物对高氯代二恶英的降解性。     

浙江省台州市电子垃圾拆解地多溴联苯醚浓度水平分布特征和迁移趋势

本研究分析了浙江省台州市电子垃圾拆解地及其周边表层土壤和大气中多溴联苯醚（PBDEs）的浓度水平.结果表明,台州市峰江和滨海的拆解园区、农田和居住区土壤中∑₁₂PBDEs含量（以dw计）范围分别为21.8~1310 ng ·g^-1和6.19~220 ng ·g^-1,PBDEs单体分布没有显著差异.峰江和滨海两地大气中∑₁₂PBDEs质量浓度范围分别为262~3240 pg ·m^-3和840~2990 pg ·m^-3,浓度中值分别为1410 pg ·m^-3和840 pg ·m^-3（冬季）、1590 pg ·m^-3和1960 pg ·m^-3（夏季）,除去BDE209外的11种PBDEs单体分布在冬夏两季呈现显著性差异.通过土-气交换逸度分析发现峰江和滨海PBDEs在土-气分布迁移趋势上呈现一定的差异性.峰江PBDEs的迁移趋势主要以土壤挥发为主,土壤是大气中3~5溴代BDEs的排放源,温度的升高可以促进这一过程,这说明峰江土壤中PBDEs已成为污染释放源,建议应对峰江电子垃圾拆解园区土壤和附近农田开展土壤修复.滨海PBDEs的迁移趋势则主要以大气沉降为主,土壤是PBDEs主要的汇,说明滨海的拆解园成为PBDEs的新排放源.     

苯为前驱物形成二噁英的反应机理

苯作为垃圾中普遍存在的成分是形成多氯二苯并对二噁英/呋喃（PCDD/Fs）的重要前驱物之一.应用密度泛函理论（DFT）在B3LYP/6-311+G （d,p）水平上研究了苯生成PCDD/Fs的两阶段气相反应机理,获得相关基元反应的势垒与反应热.采用隧道效应校正的变分过渡态理论（VTST）对300~1300K的各基元反应进行速率常数计算.结果表明：苯的氯化过程在合成PCDD/Fs各基元反应中势垒最高,是整个过程的控速步骤;氯酚更有可能被HO·进攻氯苯发生亲核反应后经分子内脱氢形成;邻位Cl能提高芳香烃H的抽取势垒,降低分子反应活性;苯氧自由基经碳碳或碳氧耦合二聚化过程形成不同PCDD/Fs存在竞争机制.相关计算结果可以用于在总二噁英产量基础上评估由苯产生的PCDD/Fs贡献率.     

多势派氯代二噁在土壤表面的紫外光解研究

本文利用500W中压汞灯研究了二(口恶)(口英)在干燥土壤中的紫外光解.根据光解结果计算了土壤中二(口恶)(口英)的降解深度,并分析了五氯代二(口恶)(口英)(PeCDD)的光解产物.结果表明,二(口恶)(口英)在土壤表面发生了较快的光解反应,反应在2h内基本完成,降解深度为0.027mm.对PeCDD光解产物的分析结果显示,二(口恶)(口英)在土壤表面紫外光降解的主要途径为脱氯,而且脱氯优先发生在邻位上.     

Analysis of dioxin-like compounds in vegetation and soil samples burned in Catalan forest fires. Comparison with the corresponding unburned material

Only a few data are reported about the formation of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) in forest fires. However, the inventories of sources undertaken by several European and American countries consider natural fires as a possible source of PCDD/F and, in some cases, as one of the most important. In our work we have analysed vegetation and soil samples burned in four forest fires which happened in Catalonia in the summer of 1998. The concentration of dioxin-like compounds (PCDD/F, non-ortho polychlorinated bi-phenyls (PCB) and mono-ortho PCB) has been compared to the concentration present in the corresponding unburned material collected in places near the fires but not affected. The results of this preliminary study show very low concentrations in all the samples, both burned and unburned. Although a change in the profile (proportional increase of tetrachlorinated congeners in PCDD/F) is observed in burned samples compared to unburned ones, the absolute values of concentration decrease in most samples. Therefore, natural fires seem not to be an important source of dioxin-like compounds. These results will be confirmed with air emissions measurements in future studies.     

Polychlorinated dibenzo-p-dioxins and related compounds: the blood levels of young Japanese women.

We investigated PCDDs and related compounds in the blood of young Japanese women, approximately 20 years of age, who had not yet had children, and discussed how the TEQ level of PCDDs and related compounds in their blood may affect the next generation. Means of total TEQ levels were 0.063 pg/g for whole blood basis and 21 pg/g for lipid basis. TEQ of PCDDs, PCDFs and coplanar PCBs accounted for about 43, 34 and 23% of the total TEQ in the whole blood basis, respectively. In the lipid basis, their values were about 44, 34 and 22%, respectively. Previously, we investigated PCDDs and related compounds levels in mother's breast milk, lymphocyte subpopulation and thyroid function of their children, and found negative correlations between the TEQ level of PCDDs and related compounds and CD4+/CD8+, and/or the TEQ level of PCDDs and related compounds and the T₄ level in 36 mothers and children. Of these cases, the average age was approximately 28 years. PCDDs and related compounds may be related to immunopathy, such as atopic dermatitis. The effects of PCDDs and related compounds on babies of young Japanese women are important and must be further evaluated.     

焦化废水中几种难降解有机物的厌氧生物降解特性

在试验室条件下,采用厌氧间歇试验,分别研究了焦化废水中几种有代表性的难降解有机物——喹啉、吲哚、吡啶、联苯的厌氧生物降解特性.文中突出了以厌氧预处理改善焦化废水中难降解有机物生物降解性的工程实用背景,对这四种有机物的厌氧处理的动力学特性、共基质作用、厌氧处理下去除效果的改善等,进行了较为深入的研究.