Removal of PCDD/Fs and PCBs from sediment by oxygen free pyrolysis

Few studies have dealt on the evaluation of volatilization and decomposition reactions of dioxins from sediment by oxygen free pyrolysis. In this study, the performance of pyrolysis on the removal of dioxins from sediment was investigated. Dioxin concentrations of the raw sediment and the solid residues after pyrolysis were analyzed at different conditions. Results showed a removal efficiency of 99.9999% for total dioxins at 800℃ and retention time of 30 min. All the polychlorinated dibenzo-furans （PCDFs） have been removed and were not formed in the solid residues at the retention time range of 30-90 min at 800℃. Close to 100% removal of polychlorinated dibenzo-p-dioxins （PCDDs） was also achieved. Only trace PCDDs were detected in the solid yields at a retention time of 60 min. The highest removal efficiency of polychlorinated biphenyls （PCBs） was more than 99.9994% at a retention time of 30 min. During cooling period following pyrolysis, however, the concentration of total dioxins in solid residues increased 130 times as compared to that of the raw sediment under air atmosphere. This confirmed that some complex reactions do occur to form PCDD/Fs and PCBs from 800 to 400℃ in the presence of oxygen. Oxygen-free atmosphere therefore can prevent formation of dioxin during thermal process thus generating clean solid residues.     

改进后EROD法与仪器分析法应用比对研究

环境二(恶)英类污染物受到广泛关注,目前常用的二(恶)英类物质检测方法有仪器分析法(高分辨率气相色谱-高分辨率质谱法)和生物检测法.生物检测法具有便捷高效、成本低廉等优点,但其测定值普遍高于仪器分析法,关键原因是生物检测法在前处理阶段未能完全消除非二(恶)英类物质的干扰.改进了传统7-乙氧基-3-异吩恶唑酮-脱乙基酶(...     

碳酰肼对烧结过程二噁英生成的抑制作用

研究了碳酰肼对钢铁厂烧结工序产生的二噁英的抑制效果。结果表明,添加了0.01%(质量分数,下同)、0.02%、0.05%、0.10%的碳酰肼之后,二噁英的排放质量浓度降为0.560、0.506、0.270、0.174ng-TEQ/m3,相对于基准值(0.821ng-TEQ/m3)大幅减少。碳酰肼对二噁英的从头合成以及前驱物生成都能起到一定的抑制效果。碳酰肼与Cu2+结合生成稳定的氮化物,削弱Cu2+的催化活性;与HCl反应,减少了生成二噁英的氯源;对FeCl3、CuCl2的催化活性也会产生影响。碳酰肼添加后,对多氯代二苯并呋喃(PCDFs)生成中高氯代二噁英的脱氯行为也有明显的抑制。     

PBDD/F impurities in some commercial deca-BDE

The study presented the concentrations and distributions of polybrominated dibenzo-p-dioxins and polybrominated dibenzofurans (PBDD/Fs) as impurities in some commercial decabromodiphenyl ether (DBDE) mixtures that were produced by several manufacturers. The total concentrations of 12 2,3,7,8-substituted tetra- to octa-BDD/F congeners were found to be in the range of 3.4-13.6 (mean 7.8) μg/g, averagely accounting for 99% of total PBDD/Fs. OBDF was the prevailing congener, followed by 1,2,3,4,6,7,8-HpBDF. In addition, OBDD and 1,2,3,4,7,8-HxBDF were also obviously detectable. The total concentrations of PBDD/Fs varied both between the manufacturers and between the lots. On the basis of the global demand for the commercial DBDE in 2001, the annual potential emissions of PBDD/Fs were calculated coarsely to be 0.43 (range: 0.21-0.78) tons. The major dioxin congeners, OBDF and 1,2,3,4,6,7,8-HpBDF, presenting in DBDE, were estimated to be formed from BDE-209, BDE-206, and/or BDE-207 via an intra-molecular elimination of Br₂/HBr.     

Emission factors for PCDD/PCDF and dl-PCB from open burning of biomass

The Stockholm Convention on Persistent Organic Pollutants includes in its aims the minimisation of unintentional releases of polychlorinated dibenzo-dioxins and dibenzofurans (PCDD/PCDF) and dioxin like PCB (dl-PCB) to the environment. Development and implementation of policies to achieve this aim require accurate national inventories of releases of PCDD/PCDF/dl-PCB. To support this objective, the Conference of Parties established a process to review and update the UNEP Standardized Toolkit for Identification and Quantification of Dioxin and Furan Releases. An assessment of all emission inventories was that for many countries open burning of biomass and waste was identified as the major source of PCDD/PCDF releases. However, the experimental data underpinning the release estimates used were limited in number and, consequently, confidence in the accuracy of the emissions predictions was low. There has been significant progress in measurement technology since the last edition of the Toolkit in 2005. In this paper we reassess published emission factors for release of PCDD/PCDF and dl-PCB to land and air.In total, four types of biomass and 111 emission factors were assessed. It was found that there are no systematic differences in emission factors apparent between biomass types or fire classes. The data set is best described by a lognormal distribution. The geometric mean emission factors (EFs) for releases of PCDD/PCDF to air for the four biomass classes used in the Toolkit (sugarcane, cereal crops, forest and savannah/grass) are 1.6 μg TEQ (t fuel)⁻¹, 0.49 μg TEQ (t fuel)⁻¹, 1.0 μg TEQ (t fuel)⁻¹ and 0.4 μg TEQ (t fuel)⁻¹, respectively. Corresponding EFs for release of PCDD/PCDF to land are 3.0 ng TEQ (kg ash)⁻¹, 1.1 ng TEQ (kg ash)⁻¹, 1.1 ng TEQ (kg ash)⁻¹ and 0.67 ng TEQ (kg ash)⁻¹. There are now also sufficient published data available to evaluate EFs for dl-PCB release to air for sugarcane, forest and grass/savannah; these are 0.03 μg TEQ (t fuel)⁻¹, 0.09 μg TEQ (t fuel)⁻¹ and 0.01 μg TEQ (t fuel)⁻¹, respectively. The average EF for dl-PCB release to land is 0.19 ng TEQ (kg ash)⁻¹. Application of these EFs to national emissions of PCDD/PCDF for global estimates from open burning will lower previous estimates of PCDD/PCDF releases to air and to land by 85% and 90%, respectively. For some countries, the ranking of their major sources will be changed and open burning of biomass will become less significant than previously concluded.     

Research on low emission MSW gasification and melting system

In order to eliminate secondary pollution caused by municipal solid waste (MSW) incineration, a MSW gasification and melting process is proposed. The process is expected to reduce the emission of pollutants, especially heavy-metals and dioxins. In this paper, the combustible components of MSW and simulated MSW were gasified in a lab-scale fluidized bed at 400°C–700°C when the excess air ratio (ER) was between 0.2 and 0.8. The experimental results indicated that the MSW could be gasified effectively in a fluidized bed at approximately 600°C–700°C when excess air ratio was 0.2–0.4. The melting characteristics of two typical fly ash samples from MSW incinerators were investigated. The results indicated that fly ash of pure MSW incineration could be melted at approximately 1,300°C and that of MSW and coal co-combustion could be melted at approximately 1,400°C. When temperature was over 1,100°C, more than 99.9% of the dioxins could be decomposed and most of the heavy-metals could be solidified in the slag. Based on the above experiments, two feasible MSW gasification and melting processes were proposed for low calorific value MSW: (1) sieved MSW gasification and melting system, which was based on an idea of multi-recycle; (2) gasification and melting scheme of MSW adding coal as assistant fuel. __________ Translated from Environmental Science, 2006, 27(1): 69–73 [译自: 环境科学]     

新型污染物卤代咔唑的环境行为及生态毒理效应

卤代咔唑(PHCs)是一类与多氯二苯并呋喃结构相类似的新型环境有机污染物.单种卤素取代的PHCs具有135个同系物.绝大多数PHCs不是人类合成化学品或工业品.虽然20世纪80年代即首次在环境中发现PHCs,但直到本世纪这类化合物才逐渐引起人们的关注.近年来,20余种PHCs在河流湖泊沉积物和土壤中被陆续检出.另外,PHCs具有类二噁英毒性、持久性和生物累积性.作为一类新型污染物,PHCs的环境行为研究目前相对较少.因此,了解PHCs的环境分布、来源和生态毒理效应对正确认识这类化合物的环境风险具有重要意义.本文综述了PHCs的环境分布、来源、分析方法和生态毒理效应,并对其未来的研究发展方向作了展望.     

Experimental study on MSW gasification and melting technology

In order to develop municipal solid waste (MSW) gasification and melting technology, two preliminary experiments and a principle integrated experiment were fulfilled respectively. The gasification characteristics of MSW are studied at 500-750℃ when equivalence ratio (ER) was 0.2-0.5 using a fluidized-bed gasifier. When temperature was 550-700℃ and ER was 0.2-0.4, low heat value (LHV) of syngas reaches 4000-12000 kJ/Nm3. The melting characteristics of fly ash were investigated at 1100-1460℃ using a fixed-bed furnace. It was proved that over 99.9% of dioxins could be decomposed and most heavy-metals could be solidified when temperature was 1100-1300℃. The principle integrated experiment was carried out in a fluidized-bed gasification and swirl-melting system. MSW was gasified efficiently at 550-650℃, swirl-melting furnace maintains at 1200-1300℃ stably and over 95% of fly ash could be caught by the swirl-melting furnace. The results provided much practical experience and basic data to develop MSW gasification and melting technology.     

二恶英类毒理学研究新进展

二恶英类的毒理学研究已有30多年的历史,在一系列二恶英类污染事件和国际公约的推动下,近年来二恶英类毒理学研究成为备受关注的热点.综述了近年来二恶英类毒理学研究的一些新的观点和发现,涵盖了分子毒性机理、致癌毒性、非致癌毒性和非致癌剂量-效应风险度评价方法等诸多领域,其中TCDD毒性效应的负反馈调节机制研究和对人体健康非致癌效应的影响引起了国内外广大毒理学研究工作者的关注.在总结前人研究的基础上对二恶英类毒理学研究今后的发展进行了展望.     

五氯酚钠及二(口恶)(口英)残留毒物对人外周血淋巴细胞的影响

采用彗星试验和微核试验,协同探索了五氯酚钠(Na-PCP)、二(口恶)(口英)类物质联合作用对血吸虫病流行区和正常生活区的人体外周血淋巴细胞影响效应.结果表明,实际用药区居民的外周血淋巴细胞以及用五氯酚钠与二(口恶)(口英)类物质联合作用处理过的正常人外周血淋巴细胞,其彗星率与微核率均高于对照组,在一定浓度范围内有剂量效应关系;基本的联合毒性作用推测为Na-PCP中的杂质PCDs与PCDFs等多种化学物质会损伤人体外周血淋巴细胞的DNA,其毒性作用比单一的二(口恶)(口英)类物质作用强.