室内环境中持久性卤代有机污染物的人体暴露及潜在生殖健康影响

卤代持久性有机污染物(Hal-POPs),如多溴联苯醚(PBDEs)、多氯联苯(PCBs)、滴滴涕(DDT)等是环境中广泛存在的全球性有机污染物,同时它们又是内分泌干扰物,是威胁人类生殖健康的重要因素之一。由于人们每天约有80%以上的时间在室内度过,且室内环境是Hal-POPs人体暴露的主要来源之一,因此室内环境中Hal-POPs对人体内分泌系统的干扰作用及其机理等问题亟待研究,但目前这方面的研究很有限。本文通过综述Hal-POPs在室内环境中的赋存水平和在人体体内的负荷水平及其半衰期,探讨了其对人体内分泌系统尤其是男性生殖健康的影响情况及其可能的机理,并分析了目前研究的不足之处及研究前景,为进一步开展这方面的研究提供借鉴。     

Inter-species differences for polychlorinated biphenyls and polybrominated diphenyl ethers in marine top predators from the Southern North Sea: Part 2. Biomagnification in harbour seals and harbour porpoises

Harbour porpoises (Phocoena phocoena) and harbour seals (Phoca vitulina) were found to differ in the ability to metabolize polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Biomagnification factors (BMFs), calculated between both predators and their prey (sole - Solea solea and whiting - Merlangius merlangus), had a large range of variation (between 0.5 and 91 for PCBs and between 0.6 and 53 for PBDEs). For the higher chlorinated PCBs and the highest brominated PBDEs, the BMF values in adult males were significantly higher than in the juvenile individuals of both species. BMF values of hexa- to octa-PCBs were the highest, suggesting reduced ability to degrade these congeners. Harbour porpoises had higher BMFs for lower chlorinated PCBs and for all PBDEs compared to harbour seals. Other factors, which may influence biomagnification, such as the octanol-water partition coefficients and the trophic level position measured through stable isotope (δ¹⁵N) analysis, were found to be of lesser importance to predict biomagnification in the studied food chain.     

Biomagnification of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls in a highly contaminated freshwater food web from South China

To evaluate the biomagnification extent of polybrominated diphenyls ethers (PBDEs) and polychlorinated biphenyls (PCBs) in a highly contaminated freshwater food web from South China, trophic magnification factors (TMFs) for 18 PBDE congeners and 53 PCB congeners were calculated. The TMF values ranged 0.26-4.47 for PBDEs and 0.75-5.10 for PCBs. Forty-five of 53 PCBs and BDEs 47, 100 and 154 had TMFs greater than one, suggesting their biomagnification in the present food web. The TMFs for PBDEs were generally smaller than those for PCBs with the same degree of halogenation, indicating a lower biomagnification potential for PBDEs compared to PCBs. For PCBs, it followed a parabolic relationship between TMFs and log K_OW (octanol-water partition coefficient). However, this relationship was not significant for PBDEs, possibly due to the more complex behaviors of PBDEs in the food web (e.g., metabolism), compared to that of PCBs.     

Particle-size distribution and gas/particle partitioning of atmospheric polybrominated diphenyl ethers in urban areas of Greece

Ambient concentrations, gas/particle partitioning and particle-size distribution of polybrominated diphenyl ethers (PBDEs) were investigated in two urban areas (Athens and Heraklion) of Greece. Atmospheric (gas + particle) concentrations of ∑PBDE varied from 21 to 30 pg m⁻³ in the center of Athens and from 4 to 44 pg m⁻³ in the suburbs of Heraklion. A predominance of particulate PBDEs was observed in Athens (71-76% in particles), whereas the opposite was evident in Heraklion (69-92% in gas phase). In both urban areas, PBDE particle-size distribution featured a distinct enrichment in smaller particles. A similar trend was also observed in aerosols of a background marine site. For all sampling sites, more than 46% of ∑PBDE was associated with particles of <0.57 μm in diameter. Our results imply that particulate PBDEs may have long atmospheric residence time and they may be capable of reaching the deeper parts of the human respiratory system.     

Spatial distribution and vertical profile of polybrominated diphenyl ethers, tetrabromobisphenol A, and decabromodiphenylethane in river sediment from an industrialized region of South China

Polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol A (TBBPA), and decabromodiphenylethane (DBDPE) were detected in fifteen surface sediments and two sediment cores collected from a river in one heavily industrialized region of South China. TBBPA and DBDPE were detected with concentrations ranging from 3.8 to 230 ng/g dw and from 23 to 430 ng/g dw, respectively. Σtri-hepta-BDEs and Σnona-deca-BDEs ranged from 0.7 to 7.6 ng/g dw and from 30 to 5700 ng/g dw, respectively. Σtri-hepta-BDEs showed an increasing trend whereas for Σnona-deca-BDE two sediment cores revealed a decreasing trend in more recent sediment layers which may attributed to the introduction of DBDPE. The rapid increasing trend for TBBPA and DBDPE in recent sediment layers well reflected the rising demand of these two compounds in study area.     

Distribution of polybrominated diphenyl ethers in breast milk from North China: Implication of exposure pathways

The breast milk concentrations of polybrominated diphenyl ethers (PBDEs; sum of eight congeners: BDE-28, 47, 99, 100, 153, 154, 183 and 209) were determined (by high resolution gas chromatographic high resolution mass spectrometry) in samples from primiparous women collected in 2006 in Tianjin, China. Dietary and lifestyle habits of the participants were obtained by questionnaires. The median total PBDE concentration (including BDE-28, 47, 99, 100, 153, 154, 183) was 2500 pg g⁻¹ lipid weight, ranging from 1700 to 4500 pg g⁻¹ lipid weight. These levels were in the same range as those from Europe and Japan but much lower than those from North America. The congener profile in China was also different from other countries. The contribution of BDE-28 was around 15%, much higher than any other country, implying that a different Penta-BDE formulation might be used in the Chinese market. The lower ratio of the sum of BDE-47, 99, and 100 to the sum of BDE-153 and 154 suggested that Octa-products were in more demand in China. A significant correlation was found between a woman’s PBDE concentration and the time she used electronic appliances (h/d). This implies that electronics are a potential source of PBDEs to people. Inhalation or ingestion of particulate matter (such as dust) may also be an important exposure pathway. There was no significant correlation between the PBDE concentration and the consumption of meat, fish, and milk. Further research is needed to determine the specific contribution of each exposure route and their health effects.     

Levels and congener profiles of PCDD/Fs, PCBs and PBDEs in seafood from China

A nationwide investigation into polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) in market seafood was conducted for the first time in this study. Total PCDD/F concentrations in fatty fish ranged from 0.13 to 8.64 pg g⁻¹ wet weight (mean 2.05 pg g⁻¹ wet weight), total PCB concentrations ranged from 38.9 to 3514 pg g⁻¹ wet weight (mean 1133 pg g⁻¹ wet weight), and total PBDE concentrations ranged from 42.8 to 913 pg g⁻¹ wet weight (mean 322 pg g⁻¹ wet weight). Corresponding mean toxicity equivalent (TEQ) values for total PCDD/F and dioxin-like PCB were 0.25 pg g⁻¹ wet weight (WHO 98-TEQ) and 0.32 pg g⁻¹ wet weight (WHO 98-TEQ), respectively. OCDD, PCB-138 and PBDE-47 were the dominant compounds according to their respective congeners. WHO 98-TEQ _{PCDD/PCDF/PCB} for fatty fish and shell fish were 0.60 and 0.070 pg g⁻¹ wet weight, respectively, lower than the standard set by the European Commission. The contamination levels and profiles were compared with those documented in previous publications.     

Emission estimation and congener-specific characterization of polybrominated diphenyl ethers from various stationary and mobile sources

Here we show that combustion sources, including waste incinerators, metallurgical processes, power-heating systems and so on, are also important emitters of polybrominated diphenyl ethers (PBDEs) to the atmosphere. Geometric mean PBDE concentrations in the stack flue gases of the combustion sources ranged from 8.07 to 469 ng/Nm³. The sinter plants (24.7 mg/h), electric arc furnaces (EAFs) (11.3 mg/h) and power plants (50.8 mg/h) possessed the largest PBDE emission rates, which were several orders higher than those of the other reported sources. The occurrences of the PBDEs in the flue gases of the power plants and vehicles, as well as their PBDE concentrations statistically highly correlated with combustion-originated PCDD/Fs, revealing that PBDEs should be the products of combustion. The ranking of major PBDE emission sources in Taiwanese PBDE inventory for combustion sources was power plants (30.85 kg/year), vehicles (14.9 kg/year) and metallurgical processes (5.88 kg/year).     

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in waterbird eggs of Hong Kong, China

Concentrations of PCDD/Fs, PCBs and PBDEs were measured in 56 egg samples collected from waterbirds of different species (Great Egret, Little Egret, Night Heron and Chinese Pond Heron) from different regions of Hong Kong (Ho Sheung Heung, Mai Po Village and Mai Po Lung Village) during 2000 and 2006. Dominance of 2,3,4,7,8-PeCDF indicates a signature associated with commercial usage of PCBs. Although no significant variations were observed within- and between-site in the levels of PCDD/Fs, coplanar PCBs and PBDEs, the concentrations of coplanar PCBs were much higher than PCDD/Fs. Similarity in composition profiles of PCDD/F and coplanar PCBs from different egretries is possibly associated with non-point sources of these contaminants to Hong Kong. Predominant accumulation of BDE-47, BDE-99 and BDE-100 suggested the penta-BDE technical mixtures usage in Hong Kong and its vicinity. Toxic equivalency and Monte Carlo simulation technique showed potential risks on waterbirds due to their exposure to PCDD/Fs.     

Assessment of characteristic distribution of PCDD/Fs and BFRs in sludge generated at municipal and industrial wastewater treatment plants

The presence of polychlorinated dibenzo-p-dioxins and furan (PCDD/Fs) and brominated flame retardants (BFRs) in sludge generated at municipal wastewater treatment plants (MWTPs) and industrial wastewater treatment plants (IWTPs) was investigated. The concentrations of these pollutants were in the following ranges: 5.38-7947 ng kg⁻¹ dw (0.02-49.9 ng WHO-TEQ kg⁻¹ dw) for 17 PCDD/Fs, 17.5-66 761 μg kg⁻¹ dw for 27 polybrominated diphenyl ethers (PBDEs), 1.55-29 604 μg kg⁻¹ dw for hexabromocyclododecanes (HBCDs) (α-, β-, and γ-diastereomers), and 4.01-618 μg kg⁻¹ dw for tetrabromobisphenol A (TBBPA). Generally, the levels of each compound in the sewage-sludge samples were higher than those in the industrial-sludge samples with some exceptions. The characteristic distribution profiles of target compounds were observed for different types of sludge and different sources of wastewater. High-chlorinated PCDD/Fs were dominant in all samples except those from the textile industry. The distribution of the BFRs in industrial-sludge samples varied, whereas that of the BFRs in sewage-sludge samples was consistent. The proportion of penta-BDEs in sewage sludge was higher than that in industrial sludge, even though BDE-209 was the most dominant congener in all the samples. For HBCDs, the distribution of diastereomers (α-, β-, and γ-HBCD) was similar across sludge samples that had the same source of wastewater and treatment processes.