持久性有机污染物(POPs)的环境问题与研究进展

对持久性有机污染物(persistentorganicpollutants:POPs)的定义、来源和特征进行了介绍。阐述了POPs对环境安全性构成威胁的原因。分析了持久性有机污染物,特别是12类优先控制的"dirtydozen"的环境污染状况,并分析了这些物质在全球大气、水体和土壤中存在的量和来源。这些物质在不同生物体内的浓度存在差异,反映出它们在食物链上的生物累积和放大,也加剧了对环境和人体的毒害作用。总结回顾了有关POPs的相关基础研究,并对将来继续深入研究和对环境监测的指导意义进行了展望。     

Determination of PCDDs,PCDFs, PCBs and HCB emissions from the metallurgical sector in Poland

Background The aim of the project was to measure the actual emissions of PCDD/F, PCBs and HCB from 20 selected metallurgical installations in Poland, in order to update the national inventory of dioxin emission from metallurgical industry for developing a strategy for dioxins and furans emission abatement from the subject facilities (UNEP 2005). Methods Sampling methodology used in this work was developed at the Cracow University of Technology because of the complexity of simultaneous sampling and determining PCDFs, PCDDs, PCB and HCB. For the determination a GC-MS/MS system was used. Results and Discussion Results from the work indicate that the highest dioxins and PCB concentrations were recorded for iron ore sintering plants at 1.10–1.32 ng total¹ TEQ/Nm³ followed by aluminium scrap melting at 0.03–0.66 ng total TEQ/Nm³. The highest HCB concentrations at 613–1491 ng/Nm³ were also recorded for iron ore sintering plants, whereas at aluminium plants the HCB concentrations were in the range of only 10.1–22.7 ng/Nm³. Conclusions The above investigations indicate that secondary aluminium production is the most significant dioxins source, if calculated as emission factor values. However, iron ore sintering plants are operating at much higher production capacity, causing this process to become the major source of dioxins, PCB and HCB pollution to the atmosphere in Poland. Recommendations and Perspectives Based on the performed tests and the environmental reviews of selected plants several recommendations were formulated for the reduction of generation or of emission of these pollutants from iron ore sintering plants, electric arc furnace steel production processes, hot-blast furnace operations, secondary aluminium smelting and primary zinc production from zinc cathodes.     

Congener profile, occurrence and estimated dietary intake of dioxins and dioxin-like PCBs in foods marketed in the Region of Valencia (Spain)

During 2006-2008, a monitoring program was conducted on 29 target compounds, including PCDD/Fs and dl-PCBs, comprising 150 randomly collected individual food samples marketed in the Region of Valencia, Spain, grouped into 8 categories (vegetables, cereals, fats and oils, eggs, milk and dairy products, fish products, meat and meat products and fish oil). For PCDD/Fs, the highest frequency of detection corresponds to 1,2,3,4,6,7,8-HpCDD, OCDD, 2,3,4,7,8-PeCDF; and PCBs 118, 105 and 156 were the more frequent dl-PCBs. The food groups presenting higher contamination, expressed as toxic equivalents (WHO-TEQs), were fish oil (6.38 pg WHO-TEQ g⁻¹ fat), fish (1.21 pg WHO-TEQ g⁻¹ w.w.) and milk and dairy products (0.90 pg WHO-TEQ g⁻¹ fat). Of all analysed samples, only two fish oils presented levels higher than the EU limits for total WHO-TEQ. The average PCDD/Fs and dl-PCBs intakes were estimated as 2.86 pg WHO-TEQ kg⁻¹ b.w. d⁻¹ and 4.58 pg WHO-TEQ kg⁻¹ b.w. d⁻¹, for adults and children, respectively, using the deterministic method for chronic exposure. The main contributors to total intake for adults were fish (59%), milk and dairy products (19%), and fat and oils (9%). The average daily intake for adults (2.86 pg WHO-TEQ kg⁻¹ b.w. d⁻¹) is within range of TDI recommended by the WHO (1-4 pg WHO-TEQ kg⁻¹ b.w. d⁻¹), and slightly above the TWI and PTMI adopted by SCF and JECFA respectively.     

Trend studies of polychlorinated biphenyls, dibenzo-p-dioxins and dibenzofurans in human milk

Human milk has been used in studies of long-term changes in the concentrations of organochlorine contaminants in mothers from the Stockholm region. The previously observed decline (1972 to 1985) in the levels of polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) seems to have ceased for certain compounds since the levels were about the same in samples collected in 1985 and 1989. Calculating with the proposed toxicity equivalency factors for the different congeners of PCDDs, PCDFs and PCBs it is seen that the congeners of PCBs contribute more to the possible toxicity than those of PCDDs and PCDFs. The mono-ortho substituted congener 2,3′,4,4′,5-pentachlorobiphenyl (IUPAC No. 118) contributes with the largest part.     

Specific biomagnification of polychlorinated dibenzo-p-dioxins and dibenzofurans in tufted ducks (Aythya fuligula), common cormorants (Phalacrocorax carbo) and their prey from Lake Shinji,Japan

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs) were detected in waterfowl such as common cormorants, tufted ducks, and their prey, namely fish and bivalves from Lake Shinji, Japan. The concentration of total PCDDs/DFs-TEQ was found to be higher in the muscle tissues of common cormorants than in those of tufted ducks. The results of hierarchical cluster analysis implied that the residue distribution pattern of PCDD/DF homologues was considerably different between these two species. Furthermore, biomagnification factors (BMFs) were estimated from bivalves as prey to tufted duck muscles as target organs. Despite the highest concentrations of 1,3,6,8- and 1,3,7,9-TeCDD in tufted ducks and their prey, however, the BMFs of these isomers were calculated to be lower than those of the toxic 2,3,7,8-substituted PCDDs/DFs. On the other hand, log BMF of toxic 2,3,7,8-substituted PCDDs/DFs were significantly higher for lower chlorinated isomers than those of the higher chlorinated isomers. The biota-sediment accumulation factors (BSAFs) of PCDDs/DFs were also estimated using shijimi clam and fish samples against sediment from Lake Shinji. The average BSAFs were estimated and ranged from 4.0×10⁻³ to 2.2×10⁻¹ and 2.0×10⁻⁴ to 2.0×10⁻¹ for bivalve and fish samples, respectively. Based on calculated BMFs and BSAFs, the total PCDD/DF-TEQ levels in the tufted duck were estimated to have been lowest (2.0 pg TEQ/g dry weight basis) in 1947 and highest (9.8 pg TEQ/g) in 1971.     

Effects of copper chloride on formation of polychlorinated dibenzo-p-dioxins in model waste incineration

Combustion experiments in a laboratory-scale fluidized-bed reactor were conducted to elucidate the effects of copper chloride as a catalyst on polychlorinated dibenzo-p-dioxins (PCDDs) formation in municipal waste incineration. We used model wastes with and without copper chloride (CuCl₂ · 2H₂O), both of which contained polyvinyl chloride as a chlorine source. Combustion temperature was set to 900 °C, and the amount of air supplied was twice the stoichiometric ratio. The experimental setup was carefully planned to suppress the influences of experimental conditions except the waste composition. Results of these experiments showed that copper chloride in the waste increased the amount of PCDDs formed and made the homologue profile to shift towards the highly chlorinated species. Copper chloride contributes to the PCDDs formation by promoting chlorination, whereby the reaction is important in that organic matter is chlorinated directly by copper compounds. Copper chloride did not exert a great influence on the isomer distribution patterns of PCDDs, while there appeared a significant difference in the case of PCDFs. This points out the difference of the major formation mechanisms between PCDDs and PCDFs. PCDDs are less formed by the catalytic reactions from carbon/polycyclic aromatic hydrocarbons than PCDFs in our experimental conditions.     

Levels and homologue profiles of PCDD/Fs in sediments along the Swedish coast of the Baltic Sea

Background, aim, and scope  The primary aim of this study was to explore the variations in PCDD/F levels and homologue profiles of Baltic surface sediments by comprehensively analyzing polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in samples from a large number of sites, encompassing not only previously known hotspot areas, but also sites near other potential PCDD/F sources, in pristine reference areas (in which there was no industrial activity) and offshore sites. Materials and methods  Surface sediment samples (146 in total) were collected at various points along the Swedish coast and offshore areas. In addition, bulk deposition was sampled, monthly, at a single site in northern Sweden during 1 year. The concentrations of tetra- through octa-substituted CDD/Fs were determined in both matrices. Results  Highly elevated concentrations of PCDD/Fs were found at many sites in coastal areas and concentrations were also slightly elevated in some offshore areas. Homologue profiles varied substantially amongst samples from coastal sites, while those from offshore and other pristine sediments were relatively similar. The offshore sediments showed different profiles from those observed in the deposition samples. Sediment levels of PCDD/Fs were not generally significantly correlated to organic carbon levels, except in some pristine areas. Comparison of data obtained in this and previous studies suggest that both their levels and profiles are similar today to those observed 20 years ago in coastal and offshore areas. The only detected trend is that their levels appear to have decreased slightly in the offshore area of the Bothnian Sea. Discussion  The localization of hotspot areas along the coast, the lack of consensus between PCDD/F profiles of sediments and general background, and their weak correlations with organic carbon suggest that PCDD/Fs in the study area largely originate from local/regional emissions. However, due to complicating factors such as sediment dynamics and land upheaval, it is not possible to conclude whether these pollutants derive from recent emissions or from a combination of recent emissions and re-distribution of previous inputs. Conclusions  The results show that: elevated levels of PCDD/Fs are present in both coastal and offshore areas of the Baltic Sea, the major hotspots are close to the shore, and there are large variations in profiles, indicating that local emissions are (or have been) the major causes of pollution. Recommendations and perspectives  In order to identify other hotspot areas and trace sources, comprehensive analysis of PCDD/Fs in surface sediments is needed in all areas of the Baltic Sea that have not been previously investigated. The high levels of PCDD/Fs observed in surface sediments also indicate a need to elucidate whether they are due mainly to current emissions or a combination of recent pollution and re-distribution of historically deposited pollutants. To do so, better understanding of sediment dynamics and present-day inputs, such as riverine inputs, industrial effluents, and leakage from contaminated soil is required. There are indications that contaminated sediments have a regional impact on fish contamination levels. However, as yet there is no statistically robust evidence linking contaminated sediments with elevated levels in Baltic biota. It should also be noted that the Baltic Sea is being massively invaded by the deep-burrowing polychaete Marenzielleria ssp., whose presence in sediments has been shown to increase water concentrations of hydrophobic pollutants. In awareness of this, it is clear that high levels in sediments cannot be ignored in risk assessments. In order to investigate the emission trends more thoroughly, analysis of PCDD/Fs in offshore sediment cores throughout the Baltic Sea is also recommended. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Laboratory-scale study of the suppression of PCDD/F emission during coal and MSW co-incineration

The experimental test of co-incinerating Chinese raw municipal solid waste （MSW） and coal in a laboratory-scale tubular reactor was first reported in present study, and the emission of normal gas components and the effects of the S/Cl molar ratio or coal mixing percentages on polychlorinated dibenzo-p-dioxins and dibenzofurans （PCDDs/Fs） emission were investigated and discussed. The results indicated that OCDD was the only PCDD homologues since others like TCDD-HpCDD was hardly detected, while as the categories of PCDF homologues were comparatively much more general. The amount of PCDD was much larger than that of PCDF in all operating conditions. Since ZPCDF/∑PCDD〈〈1, the dominant role of the precursor formation was proven in our experimental conductions. With increasing the coal addition to MSW （from 0 to 16%）, PCDD and PCDF were reduced considerably. Coal and MSW may suppress the PCDD/F emissions efficiently （over 95%） during the MSW incineration process. The PCDD/F suppression results of the present study could be helpful guidance to the industrial application of Chinese MSW and auxiliary coal co-incineration processes. The PCDD/F stack emission data of two industrial incinerators using co-incineration technology in China seem to have a great positive reduction of PCDDs/Fs.     

多氯二苯并-对-二噁英(PCDDs)半定量标准的制备

以热聚法合成,柱色谱纯化,配制了几种PCDDs的半定量标准,并对其进行了评价。     

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。