Thermal properties of dioxins, furans and related compounds

Vapor pressures are important parameters for modeling of environmental fate and incineration behaviour of chloro-dibenzodioxins and -dibenzofurans. Vapor pressures, enthalpies and entropies of sublimation were measured for four dibenzofurans and were compared to corresponding data on chlorodioxins. A vapor pressure correlation method, which uses the liquid phases as reference states was introduced. Boiling points, enthalpies and entropies of fusion could be calculated from the vapor pressure data by this method. The determined parameters were correlated with the degree of chlorine substitution and the correlations permit the estimation of boiling points, enthalpies of fusion and of sublimation pressures of n-chlorodioxins and -furans of known melting points. The predicted vapor pressures of 2,3,7,8-TCDD were found to be in good agreement with literature reportings.     

Unimolecular reaction rate theories of chlorinated dioxins and related compounds

The importance of reaction-rate theories is outlined and a short review is given over the main theories of unimolecular reactions. A new approach along the lines of the Slater theory is presented. Results of molecular decomposition rates for a chlorinated dioxine and related compounds are presented.     

Concentrations of dioxins and related compounds in the blood of Fukuoka residents

Blood samples of 152 residents (male 75 and female 77) aged 20-60 years in Fukuoka, Japan, were analyzed for dioxin toxic compounds of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), non-ortho polychlorinated biphenyls (non-ortho PCBs) and mono-ortho polychlorinated biphenyls (mono-ortho PCBs) as well as 35 PCB congeners and 12 chlorinated pesticides by high-resolution gas chromatography/high-resolution mass spectrometry. Average concentrations of dioxin toxic equivalents (TEQ) from PCDDs, PCDFs, non-ortho PCBs, mono-ortho PCBs and their total in the blood of 152 residents were 10.28, 5.56, 7.75, 4.57 and 28.15 ppt in lipid, respectively. These total TEQ levels were comparable to the blood TEQ levels of normal Japanese (n=735). Lipid basis total TEQ levels progressively increased in the males from 17.1 ppt at age 20s to 47.5 ppt at age 50s and in the females from 19.5 ppt at age 20s to 54.5 ppt at age 50s. Dioxin toxic contribution of PCBs to total TEQ was increased from 31% at age 20s to 55% at age 50s. Average concentrations of total 35 PCBs and total 12 pesticides in the blood of 151 residents were 386 and 1079 ppb in lipid, respectively. Average concentrations (ppb in lipid) of total PCBs and total pesticides also progressively increased in the males from 213 and 444 at age 20s to 868 and 2140 at age 50s, respectively, and in the females from 199 and 588 at age 20s to 550 and 1977 at age 50s, respectively. The levels of TEQ, PCBs, hexachlorobenzene, beta-hexachlorocyclohexane, dieldrin, p,p'-dichlorodiphenyldichloroethylene, p,p'-dichlorodiphenyltrichloroethane, trans-nonachlor and cis-nonachlor were positively correlated with each other in most of the combinations, and the highest correlations (r>0.8) were observed between total TEQ and PCBs in both sexes.     

Concentration and distribution of dioxins and related compounds in human tissues

Polychlorinated dibenzo-p-dioxin, polychlorinated dibenzofuran and dioxin-like polychlorinated biphenyl concentrations in human blood, lung, liver, bile, pancreas, spleen, kidney and mesentery fat were determined to assess the concentrations and distribution of these chemicals in human tissues from 20 donors. The mean TEQ concentrations in blood, lung, liver, bile, spleen, pancreas, kidney and mesentery fat were 119, 178, 228, 50, 113, 163, 138 and 139 pg TEQ/g lipid, respectively. Parallel levels were seen in the blood, spleen, kidney and mesentery fat; in the lungs and pancreas, the levels were somewhat higher. Among the organ tissues samples, the highest concentration was observed in the liver and the lowest in the bile. Mean total-TEQ concentration of the liver was about 4.5 times higher than that of bile. Positive correlations were observed among the concentrations of dioxins in various tissues. However, the concentrations in bile were not correlated with any tissues. It is suggested that the distribution behavior of dioxin-like congeners in human tissues varies among tissues and the kinds of congeners ingested. To evaluate the relationship between the accumulation levels of dioxins and their pathophysiological significance or risk, data must be accumulated from a more extensive group of human samples.     

二噁口英及类似有毒有害物的处理技术

二(口恶、口英)、多氯联苯、多环芳香烃及化学武器等有毒有害物的处理技术已取得长足进展.这些有毒有害物的处理技术可概括为物理方法、化学方法、物理化学方法和生物降解法.本文从概念、应用场合、分解效率以及操作条件等方面对这些方法分别进行了介绍,重点介绍和评述了吸附和催化法,以及应用前景很好的生物降解技术.     

3D QSAR studies of dioxins and dioxin-like compounds using CoMFA and CoMSIA

In the present study we have performed comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) on structurally diverse ligands of Ah (dioxin) receptor to explore the physico-chemical requirements for binding. All CoMFA and CoMSIA models have given q(2) value of more than 0.5 and r(2) value of more than 0.84. The predictive ability of the models was validated by an external test set, which gave satisfactory predictive r(2) values. Best predictions were obtained with CoMFA model of combined modified training set (q(2) = 0.631, r(2) = 0.900), giving predictive residual value = 0.02 log unit for the test compound. Addition of CoMSIA study has elucidated the role of hydrophobicity and hydrogen bonding along with the effect of steric and electrostatic properties revealed by CoMFA. We have suggested a model comprises of four structurally different compounds, which offers a good predictability for various ligands. Our QSAR model is consistent with all previously established QSAR models with less structurally diverse ligands.     

Formation of chlorinated and brominated dioxins and other organohalogen compounds at the pilot incineration plant VERONA

Experiments were conducted at the VERONA pilot plant, an incineration plant with stationary grate and separate post-combustion chamber, using wood and propane as basic combustible materials and with controlled dosage of various bromine-, chlorine- and copper-containing compounds. The behaviour of the following compounds was studied in the combustion chamber, after the post-combustion chamber and after the heat exchanger: polychlorinated phenols (PCPh), polybrominated phenols (PBrPh), polychlorinated benzenes (PCBz), polybrominated benzenes (PBrBz), polychlorinated dioxins and furans (PCDD/F) and polybrominated dioxins and furans (PBDD/F). The bromine co-incineration leaded to very high bromophenol concentrations after the post-combustion chamber. The formation of brominated and mixed-halogenated phenols and the further reaction to halogenated dioxins is apparently a relevant reaction mechanism for dioxin formation in processes involving bromine. This assumption is supported by the high formation rates of PBDD/F found in the heat exchanger, which were 4-20 times higher than those of PCDD/F. Moreover, the strong correlations found between the formation rates of PCPh, PCBz and PCDD/F in the heat exchanger indicate that in addition considerable new formation of dioxins takes place through de novo synthesis. Experiments involving the variation of primary operational parameters and fuel properties have shown that the quality of post-combustion plays a much greater role than the other parameters. Furthermore, it became apparent that the congeners of the chlorophenols and of the chlorobenzenes, measured in various incineration stages, do not correlate closely with the dioxin concentrations after the heat exchanger.     

Levels of dioxins and furans in urban surface soil in Trondheim, Norway

A study was conducted on polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in surface soil in order to determine the concentration levels and possibly distinguishing between known and potential sources. The concentration levels are low (0.16-14 ng I-TEQ kg(-1)). The results show a clear pattern where the highest concentration levels were found in the oldest parts of the city. A number of sources were recognised in the soil samples through congener profiles, not all of them active, although similar congener profiles make it extremely difficult to distinguish between different sources. Estimations show that the municipal solid waste incinerator (MSWI) and domestic wood burning are the largest PCDD/F pollution sources within the area.     

Levels of dioxins, dibenzofurans and selected other chlorinated organic compounds in food from Russia

Food is considered to be the main source of dioxins (PCDDs) and dibenzofurans (PCDFs) for human intake, but there are relatively few publications reporting the levels of dioxins and furans in food samples.^(1–4) Food samples from western to eastern Russia were collected during three recent trips by one of us (AS), and tested for dioxins and dibenzofurans to provide some indication of environmental contamination. The results show that in specific food samples there are more dioxins present than dibenzofurans, but in fish samples the opposite is true. We compare the levels found in Russian food with levels found in samples from other countries, on both wet weight and lipid basis. These Russian samples show ranges similar to but slightly lower than those seen in other industrial countries.     

Contamination status of dioxins in sediment cores from the Three Gorges Dam area, China

In order to screen dioxin pollution in sediment of Three Gorges Dam (TGD) area, three sediment cores were obtained from two sites in 2010~2011; each core was divided into different samples with every 10 cm depth. Sediment dating determined by radiometry (¹³⁷Cs, ²¹⁰Pb) and concentrations of dioxins were analyzed by high-resolution gas chromatography/mass spectrometry. The results indicated: Sediment dating showed no significant difference among all the samples from the same core and the two locations (ANOVA, p?>?0.05). The total amount of polychlorinated dibenzo-p-dioxins (PCDD)/Fs in all sample ranged from 30.7 to 371 pg/g dry weight (d.w.), with the mean value of 66.2 pg/g d.w. PCDDs occupied 60.33~85.22 % of dioxins in each sample, and PCDFs contributed to a very small extend. There was no significant difference in the dioxin concentration between 2010 and 2011 and in the two locations (t test, p?>?0.05), but the vertical distribution of dioxins showed significant different in different depths. Toxic equivalent (TEQ) (WHO 2005, Humans) of samples ranged from 0.15 to 1.60 pg/g d.w.; the mean was 0.41 pg/g d.w. No significant difference was found in TEQ between 2010 and 2011(t test, p?>?0.05). It could be concluded that the distribution of dioxins showed the spatial heterogeneous which resulted from the strong mixing and sediment deposition characteristics. Dioxin concentration in sediment cores was low with very low environmental risk potential. Dioxins at the two sites had the same origin, and exogenous input was the main source. It is the first report on the dioxins concentrations in sediment cores in the TGD area.     

Removal of dioxins and related aromatic hydrocarbons from flue gas streams by adsorption and catalytic destruction

The dioxin removing capacity of the shell dedioxin system (SDDS-a Ti/V oxidative type catalyst) has been tested using the Ume? lab-scale incinerator over the temperature range 100-230 degrees C and at space velocities of 8000 and 40,000 h(-1). Other analogous organic compounds, such as PCBs, PAHs, chlorobenzenes and chlorophenols have also been investigated. Results show a high degree of dioxin removal already at 100 degrees C (82%), which occurs mainly by adsorption. When the temperature is raised a transition towards destruction is seen and at 150 degrees C, gas hour space velocity (GHSV) 8000 and at 230 degrees C, GHSV 40,000 virtually all removal is by destruction. High PCDD/F destruction efficiencies are reported (> 99.9%, based on I-TEQ); the other dioxin-related species and PAHs are also removed and destroyed to a significant extent. The SDDS has proved to be an effective means of destroying organic compounds in the gas phase, particularly dioxins, at temperatures as low as 150 degrees C.     

An intercalibration study on organobromine compounds: Results on polybrominated diphenylethers and related dioxin-like compounds

An intercalibration study on organobromine compounds has been conducted to evaluate the accuracy and reliability in the analysis of brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) and their related compounds like polybrominated and monobromo-polychlorinated dibenzodioxins and -furans (PBDDs/DFs, MoBPCDDs/DFs). This paper reports the results for these compounds in 'Mixed Standard Solutions' and 'Air-Dried Sediment'. The relative standard deviations (RSDs) for PBDEs, PBDDs/DFs and MoBPCDDs/DFs in mixed standard solutions ranged from 9% to 24%, 4% to 20% and 8% to 27%, respectively. The results of this study are better than those reported in earlier international interlaboratory studies due to general improvement in analytical methods and an increasing number of available authentic standards, particularly for PBDEs. In the analysis for higher brominated compounds such as octabromodibenzodioxin, the participants were advised to optimize the calibration curves befitting the range of concentrations found in samples because variation of relative response factors was noted. The results for 'Air-Dried Sediment' were also reasonable with RSDs from 10% to 38% for PBDEs, 8% to 38% for PBDDs/DFs and 17% to 36% for MoBPCDDs/DFs. In the sediment sample, possible errors in the sample pretreatment and/or interference by other compounds/impurities were indicated. The concentrations of pentabromodiphenylether, BDE100, varied more than the other PBDE isomers due to its poor separation in some chromatographic conditions. In addition, interference by PBDEs was observed in the analysis for PBDFs. Potential degradation/secondary formulation of PBDEs and PBDFs during the Soxhlet extraction were suggested when copper powder was added into the sediment samples. Inspite of these observations, the results in this study are better than those reported in other interlaboratory studies due to the advice given to participants for improving the results. Compared with the results for PCDDs/DFs (5-23% RSDs) and Co-PCBs (6-24% RSDs), the RSDs for most of the organobromine compounds were high, indicating an immature QA/QC approach for the analysis of PBDEs and related compounds in comparison to common chlorinated dioxins.     

汽车尾气净化催化剂涂层改性研究

汽车尾气净化催化剂的净化转化效果及其耐久性,与催化剂涂层的涂覆量以及涂层和载体的结合强度密切相关.本文研究了几种不同类型表面活性剂对浆料固体含量、涂层涂覆量以及涂层结合强度的影响.研究结果表明,不使用表面活性剂时,30%为最佳的固体含量;在使用表面活性剂的情况下,浆料的固体含量可以提高至35%.非离子型表面活性剂有助于提高催化剂涂层涂覆量,而使用离子型表面活性剂的浆料球磨过程中产生大量泡沫,无法涂覆.使用非离子型表面活性剂的催化剂涂层的结合强度最好.     

汽车尾气净化催化剂涂层改性研究

汽车尾气净化催化剂的净化转化效果及其耐久性，与催化剂涂层的涂覆量以及涂层和载体的结合强度密切相关。本文研究了几种不同类型表面活性剂对浆料固体含量、涂层涂覆量以及涂层结合强度的影响。研究结果表明，不使用表面活性剂时，30％为最佳的固体含量；在使用表面活性剂的情况下，浆料的固体含量可以提高至35％。非离子型表面活性剂有助于提高催化剂涂层涂覆量，而使用离子型表面活性剂的浆料球磨过程中产生大量泡沫，无法涂覆。使用非离子型表面活性剂的催化剂涂层的结合强度最好。     

Body burden of dioxins and dioxin-like polychlorinated biphenyls in pregnant women residing in a contaminated area

A large pentachlorophenol (PCP)-manufacturing plant located in southwestern Taiwan operated between 1965 and 1982. The present study was conducted to ascertain whether an increased body burden of dioxins existed in pregnant women living in an area of Tainan city contaminated by chemicals from this plant. Twenty-eight pregnant subjects, 21-39 years of age and residing in the study area between March and December of 2004 with a mean dwelling time of 6.07+/-6.11 years, were recruited. Concentrations of polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/Fs), and dioxin-like polychlorinated biphenyls (PCBs) in serum of recruited residents were determined. Pregnant women residing in the study area >3 years had significantly higher PCDD (7.48 versus 5.13 pg-toxic equivalents [TEQ]/g-lipid) and dioxin-like PCB (6.70 versus 3.74 pg-TEQ/g-lipid) values as compared to those residing < or = 3 years. Furthermore, dioxin concentrations increased with increasing dwelling time. Statistical analyses performed according to demographic characteristics and socioeconomic and dietary habits revealed that total TEQ values were significantly associated with fish consumption and smoking status. Dioxin congeners with greater degrees of chlorine substitution (e.g., HpCDD/F and OCDD/F) partitioned to greater degrees in the subjects of this study as compared to subjects in the general Taiwanese population. The findings of this study strongly implicate the activity of the PCP manufacturing plant in the observed increase in dioxin body burden. Investigation of the health consequences of this increased body burden is recommended.     

Biodegradability of ethylenediamine-based complexing agents and related compounds

The biological degradability (Zahn-Wellens test) of ethylenediamine derivatives with carboxymethyl and 2-hydroxyethyl groups was investigated. Mixed bacterial culture (activated sludge) was used as inoculum (non-adapted sludge and sludge adapted at different mean biomass retention time, the so-called sludge age). Biodegradability of ethylene(propylene)di(tri)amine-based complexing agents depends on the character and number of substituents and nitrogen atoms in the molecule. Tetra(penta)substituted derivatives with two or more tertiary nitrogen atoms and carboxymethyl or 2-hydroxyethyl groups in the molecule (EDTA, DTPA, PDTA, HEDTA) are very stable from an environmental point of view. On the contrary, disubstituted derivatives with two secondary nitrogen atoms in the molecule (e.g., EDDA) are potentially degradable.     

Biological remediation of explosives and related nitroaromatic compounds

Nitroaromatics form an important group of recalcitrant xenobiotics. Only few aromatic compounds, bearing one nitro group as a substituent of the aromatic ring, are produced as secondary metabolites by microorganisms. The majority of nitroaromatic compounds in the biosphere are industrial chemicals such as explosives, dyes, polyurethane foams, herbicides, insecticides and solvents. These compounds are generally recalcitrant to biological treatment and remain in the biosphere, where they constitute a source of pollution due to both toxic and mutagenic effects on humans, fish, algae and microorganisms. However, relatively few microorganisms have been described as being able to use nitroaromatic compounds as nitrogen and/or carbon and energy source. The best-known nitroaromatic compound is the explosive TNT (2,4,6-trinitrotoluene). This article reviews the bioremediation strategies for TNT-contaminated soil and water. It comes to the following conclusion: The optimal remediation strategy for nitroaromatic compounds depends on many site-specific factors. Composting and the use of reactor systems lend themselves to treating soils contaminated with high levels of explosives (e.g. at former ammunition production facilities, where areas with a high contamination level are common). Compared to composting systems, bioreactors have the major advantage of a short treatment time, but the disadvantage of being more labour intensive and more expensive. Studies indicate that biological treatment systems, which are based on the activity of the fungus Phanerochaete chrysosporium or on Pseudomonas sp. ST53, might be used as effective methods for the remediation of highly contaminated soil and water. Phytoremediation, although not widely used now, has the potential to become an important strategy for the remediation of soil and water contaminated with explosives. It is best suited where contaminant levels are low (e.g. at military sites where pollution is rather diffuse) and where larger contaminated surfaces or volumes have to be treated. In addition, phytoremediation can be used as a polishing method after other remediation treatments, such as composting or bioslurry, have taken place. This in-situ treatment method has the advantage of lower treatment costs, but has the disadvantage of a considerable longer treatment time. In order to improve the cost-efficiency, phytoremediation of nitroaromatics (and other organic xenobiotics) could be combined with bio-energy production. This requires, however, detailed knowledge on the fate of the contaminants in the plants as well as the development of efficient treatment methods for the contaminated biomass that minimise the spreading of the contaminants into the environment during post harvest treatment.     

染料废水生物降解的产物分析

介绍了含酸性蒽醌蓝324染料废水在兼氧-好氧系统中的生物转化.产物分析结果表明:80.5%的母体染料大分子能在兼氧条件下降解成较为简单的中间产物,并且这些中间产物能在好氧条件下进一步矿化.对各反应器中主要的代谢产物分别进行紫外-可见、红外(FT-IR)和高效液相色-质联谱仪(HPLC-MS)检测分析后发现,母体染料经兼氧水解首先生成1-氨基-2-羟基蒽醌以及还原态的-OH基取代蒽醌隐色体,进一步水解生成3,4-二羟基苯甲酸.再经好氧处理,降解终产物中检测到了质荷比为101、102的脂肪类碳氢化合物、胺及醇等物质,未见有共轭结构存在.