M12半自动净化法与手工净化法应用于飞灰中二噁英类检测比较

研究比较了M12半自动净化法与手工净化法应用于二噁英检测的效果。结果显示,采用高分辨气相色谱-高分辨质谱法(HRGC-HRMS)检测飞灰样品中的二噁英,手工净化法的回收率要优于M12半自动净化法的回收率,但M12半自动净化法除2种单体外,其余单体回收率均满足对二噁英的分析要求,且2种净化方法所得二噁英的总毒性当量结果相近,证明手工净化法与HRGC-HRMS联用检测飞灰中二噁英的效果较好,但M12半自动净化法也能够满足HRGC-HRMS检测二噁英的净化要求。应用酶联免疫法检测飞灰样品中二噁英的总毒性量,当样品中二噁英浓度较高时,M12半自动净化法和手工净化法净化测得结果与基准值一致性较好;当样品中二噁英浓度较低时,手工净化法检测结果与基准值差别较大,表明酶联免疫法更适合用M12半自动净化法进行净化。     

Fungal hydroxylation of polychlorinated naphthalenes with chlorine migration by wood rotting fungi

Biodegradation of the polychlorinated naphthalenes (PCNs) 1,4-dichloronaphthalene (1,4-DCN), 2,7-dichloronaphthalene (2,7-DCN), and 1,2,3,4-tetrachloronaphthalene (1,2,3,4-TCN), by the white-rot fungus Phlebia lindtneri was investigated. 1,4-DCN was metabolized to form six metabolites by the fungus. It was estimated from GC–MS fragment patterns that the metabolites were four putative hydroxylated and two dihydrodihydroxylated compounds. One of the hydroxylated products was identified as 2,4-dichloro-1-naphthol by GC–MS analysis using an authentic standard. This intermediate indicated chlorine migration in a biological system of P. lindtneri. 2,7-DCN was metabolized to five hydroxylated metabolites and a dihydrodihydroxylated metabolite. Significant inhibition of the degradation of DCNs and formation of their metabolic products was observed in incubation with the cytochrome P-450 monooxygenase inhibitor piperonyl butoxide. The formation of the dihydrodiol-like metabolites, chlorine migration and the experiment with P-450 inhibitor suggested that P. lindtneri provides hydroxyl metabolites via benzene oxide intermediates of DCNs by a cytochrome P450 monooxygenase. In addition, P. lindtneri degraded 1,2,3,4-TCN; two hydroxylated compounds and a dihydrodihydroxylated compound were formed.     

垃圾焚烧过程中二恶英污染控制技术

本文对垃圾焚烧过程中如何控制二恶英的产生及焚烧后的残渣、飞灰的处理技术进行了综合分析,并对适合我国国情的垃圾焚烧技术作了初步探讨。     

二噁污染及其在垃圾焚烧中的控制

介绍二噁的毒性及其在环境中的存在状态,并就在垃圾焚烧中如何控制二噁(口英)的产生及焚烧后残渣、飞灰的处理进行了探讨。     

Maternal exposure to high levels of dioxins in relation to birth weight in women affected by Yusho disease

Background

Studies on the association of maternal exposure to polychlorinated dibenzo-p-dioxin (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) with decreased birth weight in humans have produced conflicting results. In Japan in 1968, an accidental human exposure to rice oil contaminated with PCDDs, PCDFs, and PCBs, led to the development of Yusho disease.

Objective

The Yusho cohort was used to evaluate the effect of maternal exposure to PCDDs, PCDFs, and PCBs on birth weight.

Methods

Blood samples, obtained from 101 Yusho women (190 births) who gave birth after exposure, were analyzed for congeners of seven PCDDs, ten PCDFs, and four non-ortho PCBs.

Results

Total PCDD TEQ (adjusted beta = − 161.9 g; 95% CI, −265.3 to − 58.6), total PCDF TEQ (adjusted beta = − 105.9 g; 95% CI, −179.5 to − 32.2), and total non-ortho PCBs (adjusted beta = − 178.4 g; 95% CI, −318.3 to − 38.5) levels were inversely associated with birth weight. Significant inverse associations with birth weight were also found for total PCDD TEQ, total PCDF TEQ, and total non-ortho PCB TEQ levels among male, but not female, infants. Significant inverse associations with birth weight were also found for nine congeners among all infants; the adjusted beta coefficients were largest for 1,2,3,6,7,8-HxCDD and smallest for 2,3,4,7,8-PeCDF.

Conclusion

In the setting of exposure to high levels of dioxins, maternal blood levels of PCDDs, PCDFs and PCBs are associated with lower birth weight in Yusho patients. The association exhibited gender-specific differences, as male infants are more susceptible than females to growth restriction induced by in utero dioxin exposures.     

Novel enzymatic activity of cell free extract from thermophilic Geobacillus sp. UZO 3 catalyzes reductive cleavage of diaryl ether bonds of 2,7-dichlorodibenzo-p-dioxin

We characterized the ability of the cell free extract from polychlorinated dibenzo-p-dioxins degrading bacterium Geobacillus sp. UZO 3 to reduce even highly chlorinated dibenzo-p-dioxins such as octachlorodibenzo-p-dioxins in incineration fly ash. The degradation of 2,7-dichlorodibenzo-p-dioxin (2,7-DCDD) as a model dioxin catalyzed by the cell free extract from this strain implicates that the ether bonds of 2,7-DCDD molecule undergo reductive cleavage, since 4′,5-dichloro-2-hydroxydiphenyl ether and 4-chlorophenol were detected as intermediate products of 2,7-DCDD degradation.     

Comparison of the concentrations of polychlorinated biphenyls and dioxins in mothers affected by the Yusho incident and their children

Accumulated maternal dioxins are passed onto the fetus and neonate via the placenta and maternal milk. In Japan in 1968, an accidental human exposure to rice oil contaminated with polychlorinated biphenyls (PCBs) and other dioxin-related compounds, such as polychlorinated dibenzofurans (PCDFs), led to development of Yusho oil disease. We investigated differences in blood dioxin concentrations in mother-children pairs affected by the Yusho incident. From 2002 to 2008, blood samples were collected from 26 pairs of Yusho mothers and their children (19 mothers, 26 children). Specific congeners of seven polychlorinated dibenzo-p-dioxins (PCDDs), ten PCDFs, and four non-ortho PCBs were analyzed. The children had significantly lower TEQ concentrations of PCDDs, PCDFs, and coplanar PCBs compared to their mothers. The mother-child difference in blood concentrations varied with the congeners; the largest for 2,3,4,7,8-pentaCDF and the smallest for 1,2,3,4,6,7,8-heptaCDD. The level for 2,3,4,7,8-pentaCDF, which characterizes Yusho oil disease, was approximately 17-30 times higher in the mothers than in the general population, whereas there were no significant differences between children in the formula-fed group and the general population. In contrast, the mean level for 2,3,4,7,8-pentaCDF in the breast-fed group was approximately 1.5 times, (range 0.5-6.5 times) higher than that in the general population. Over 30 years after the Yusho incident, the mean blood dioxin levels in the offspring were only a fraction of the levels in their mothers. This is more consistent with exposure via breast milk than via transplacental transfer in the Yusho incident.     

Inhibition of PCDD/F by adding sulphur compounds to the feed of a hazardous waste incinerator

Sulphur compounds, including (NH₄)₂SO₄ and pyrite, were tested as suppressants in a hazardous waste incineration facility. The test results suggested that adding sulphur compounds only slightly reduced PCDD/F stack emissions; this restricted effect was attributed to the release of fly ash in large amounts during the sulphur adding experiments, i.e., it was due to a malfunctioning of the baghouse filter. Nevertheless, for the combined flow of flue gas + fly ash a reduction of more than 50% was achieved for the total PCDD/F concentrations and the total toxic concentrations, and an even higher inhibition capability was observed for PCDD. Also, a simulation of the thermodynamic equilibrium conditions by sulphur dioxide was conducted in the domain of experimental interest. Deactivation of catalysts, which promote PCDD/F formation, was found to be the dominant inhibition mechanism in low temperature PCDD/F formation. SO₂ could also inhibit the formation of molecular Cl₂ via the Deacon reaction, but that was not the main reason for inhibition.     

Atmospheric deposition of PCDD/Fs measured via automated and traditional samplers in Northern Taiwan

Most polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the atmosphere are bound to particles which are suspended in the atmosphere, and eventually settle on soil, vegetation, water bodies or other receptors in the environment. Monitoring atmospheric deposition fluxes (dry/wet) is important in tracing the environmental fate and behavior of PCDD/Fs. PCDD/F depositions were collected via an automated PCDD/F ambient sampler and traditional cylindrical vessels, respectively, from April 2007 to February 2008. The automated PCDD/F ambient sampler used in this study can prevent both re-suspension and photo degradation of the PCDD/Fs collected and effectively separates the PCDD/F samples into dry and wet contributions. The results indicated that the ambient PCDD/F concentrations collected using the PS-1 sampler ranged from 0.02 pg I-TEQ/m³ to 0.16 pg I-TEQ/m³ in Northern Taiwan. The results also indicated that the PCDD/F deposition flux collected using the automated PCDD/F sampler (17.5 pg I-TEQ/m² d to 25.8 pg I-TEQ/m² d) was significantly higher than that sampled with the cylindrical vessels (2.0 pg I-TEQ/m² d to 9.9 pg I-TEQ/m² d). The difference was attributed to the fact that part of the PCDD/F depositions collected using the traditional cylindrical vessels had undergone photo degradation and evaporation. In addition, the wet deposition flux of PCDD/Fs (39.4 pg I-TEQ/m² rainy day to 228 pg I-TEQ/m² rainy day) observed in this study was significantly higher than the dry deposition flux (12.3 pg I-TEQ/m² sunny day to 16.7 pg I-TEQ/m² sunny day). These results demonstrated that wet deposition is the major PCDD/F removal mechanism in the atmosphere.     

PCDD/Fs in ambient air in north-east Italy: The role of a MSWI inside an industrial area

The stack gases of a municipal solid waste incinerator (MSWI), and ambient air were sampled in four locations around the plant for the analysis of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs). The sampling area was close to an industrial area near Trieste, in north-east Italy. The purpose of the study was to estimate the impact of the MSWI emissions and to distinguish the contribution of these emissions from other potential emission sources in the industrial area.PCDD/F atmospheric concentrations were similar to those generally detected in urban–rural areas with one location about 2–3 times more contaminated than the others. Since the most contaminated location was inside the industrial area but upwind of the MSWI, principal component analysis (PCA) was used to establish whether other sources were the cause. This analysis clearly showed that a local steel plant’s emission was the main source of PCDDs/Fs in ambient air. This study highlights the usefulness of multivariate data analysis such as PCA to identify, among different potential emission sources, the one really responsible for the contamination.