塑料企业周边水体中多溴联苯醚的污染特征

多溴联苯醚(PBDEs)是一种新型的持久性有机污染物(POPs)。采用固相萃取-气相色谱法测定了某塑料企业周边及当地自然水体中的PBDEs浓度,主要针对BDE~(-1)7、28、47、66、85、99、100、138、153、154、183、203及BDE-209共13个PBDE同系物的浓度水平、组成分布和污染特征进行分析。结果显示,使用企业周边水体中除BDE-203在水体中未检出外,其余12种PBDE同系物均有不同程度的检出。Σ13PBDEs质量范围处于未检出~363 ng·L~(-1),各同系物的平均质量浓度为未检出~42.6ng·L~(-1)。其中BDE-209为最大检出质量丰度同系物,但其检出率仅为25.0%,检出率较高的同系物是BDE~(-1)7、BDE-28和BDE~(-1)00,检出率分别为75.0%、75.0%、58.3%,低溴代联苯醚的检出率显著高于高溴代联苯醚。当地自然水体中13种PBDEs均有不同程度的检出,检出浓度在0.161~1.83 ng·L~(-1)。企业周边水体中PBDEs的污染水平显著高于自然水体,是自然水体浓度的5~100倍。因此,企业周边区域水体中PBDEs的污染情况应引起相关部门关注。     

The polymorphism of the human serum paraoxonase †

The activity of paraoxonase, the enzyme which hydrolyses paraoxon, 0,0‐diethyl‐0–4‐nitrophenylphosphate, in human serum shows a genetically determined polymorphism with strong interethnic differences. The serum paraoxonase genotype has a significant influence on the paraoxon clearance. Individuals with high serum paraoxonase activity may be better protected against the toxic effects of parathion (0,0‐diethyl‐0–4‐nitrophenylthiophosphate).

In Caucasians the polymorphism is governed by two alleles. The first allele has a gene frequency p _low of 0.67 to 0.78, and is manifested in both the form of a first homozygotic group with low activities and a second heterozygotic group with medium activities. About 50% of all Europeans belong to the low activity group. The second allele with a gene frequency q _high of 0.22 to 0.33 is manifested in the second heterozygotic and a third homozygotic group with medium resp. high activities. The Hardy‐Weinberg rule for a two allele model is valid for the distribution.

The percentage of the low activity group decreases as one moves from Europe to Africa and Asia. In most of the Mongoloids and Negroids only 5 to 20% of the population can be included in the low activity group, which is not even demonstrable in Aborigines, Maoris, Tonga and some African and Indian (Central America) tribes. The validity of the Hardy‐Weinberg rule for a two‐ or three‐allele model must be rejected in non‐Caucasians.     

Indoor and outdoor air PBDE levels in a Southwestern US city

Levels of polybrominated diphenyl ether (PBDE) flame retardants have been increasing in humans and the environment for the past few decades. Human levels are markedly higher in the US than Europe. Although food appears to be a significant route of intake, food PBDE levels are not substantially higher in the US than Europe. House and office dust appear to be major routes of exposure with air believed to usually provide a lesser route of intake. Because there are very few measurements of airborne PBDE that have been performed in relevant microenvironments in the US, increased efforts to assess airborne PBDE in the US as sources of exposure are needed. This study reports, for the first time from a Southwestern US city in Texas, the results of measurements of airborne PBDE in multiple locations, two outdoor and six indoor (residential and office) from active air sampling with collection of a combination of both vapor- and particulate-phase PBDE. Higher PBDE levels were measured in indoor than outdoor air, which confirms previous findings. Of 11 measured congeners including BDE 209, total PBDE levels in two outdoor air samples were 112 and 125 pg m^?3 and the indoor air levels ranged from 175 to 1232 pg m^?3 with a median of 572 pg m^?3. These findings suggest that sources of air contamination with PBDE may be similar in Texas as elsewhere in North America. However, more sampling is required to (1) better determine if this is the case and (2) attempt to characterize potential sources of PBDE contamination in both indoor and outdoor air by analysis of congener patterns.     

Time-dependent effects of pentabrominated diphenyl ethers on gonadal hormone and genital system histology in male rats

The aim of this study was to examine the effects of pentabrominated diphenyl ethers (PBDE) on gonadal hormone levels and histology in male rats. Rats in treatment groups were orally gavaged with PBDE-99 at a dose of 120 mg?kg^?1 for 5, 15, 30, or 45 days, while controls received equal volume of corn oil. In the treated groups, changes were not found on day 5. On day 15, testicular weight increased, serum levels of estradiol (E₂) decreased, proliferation cell nuclear antigen (PCNA) positive expression was reduced, and sperms within the seminiferous tubules were damaged. On day 30, testicular weight was further increased, serum levels of testosterone (T) and E₂ decreased, PCNA positive expression was further reduced, some primary spermatocytes cells did not express, and seminiferous epithelium was degenerated. At 45 days, testicular weight decreased, levels of T, E₂ concentrations were lower, histopathologic examination revealed severe degeneration of seminiferous epithelium, and only a part of spermatogonial cells were expressed. The earliest alterations occurred at 15 days. PBDE-99 produced time-dependent reduction of gonadal hormone levels and degeneration of gonadal system histology.     

典型废旧塑料处置地土壤中多溴联苯醚污染特征

选择我国北方典型废旧塑料处置地为研究区域,对土壤中21种PBDEs(多溴联苯醚)的含量、同系物组成和分布特征进行了研究. 结果表明,该区域土壤中w(∑PBDEs)为1.25~3673.41ng/g,平均值为749.29ng/g,其中w(BDE209)占w(∑PBDEs)的92%以上. 整体上,处置作坊内土壤中w(∑PBDEs)明显高于作坊间道路土壤和处置地周边土壤. 塑料中添加的十溴联苯醚工业品是该区域土壤中PBDEs的主要来源. 该区域土壤PBDEs污染水平与我国电子废物集中处置场地相当,高出我国一般城市及工业城市土壤1~3个数量级,是我国另一类PBDEs高污染区,其环境风险性应引起足够的重视.      

Polybrominated diphenyl ether (PBDE) levels in the blood of pure vegetarians (vegans)

Intake of many persistent organic pollutants (POPs) including dioxins, dibenzofurans and PCBs is almost exclusively from gastrointestinal ingestion of animal fats in the diet. With polybrominated diphenyl ether (PBDE) brominated flame retardants (BFRs), no consensus exists at present as to the extent of intake from food, from indoor dust or other routes of intake. Vegans, or pure vegetarians, were previously found to have low body burden of dioxins and dibenzofurans in blood. Data reported here for the first time show a trend towards lower PBDE levels with longer time periods without ingestion of food of animal origin in 8 adult residents of the United States. A stronger relationship between lower PBDE levels and time without meat, specifically, is consistent with substantial PBDE intake from meat relative to fish or dairy products in Americans. These vegans had somewhat lower PBDE levels with a range 12.4–127 and a median 23.9?ppb than published reports of US general population samples which had a range of 4–366 and median of 26?ppb. Our findings suggest that food of animal origin may be a major but not the sole contributor to human body burden of PBDEs.     

Time-dependent effects of pentabrominated diphenyl ether (PBDE) on thyroid hormones and histology in rats

In order to examine the time-dependent effects of pentabrominated diphenyl ether (BDE-99) on thyroid hormones levels and histological structure in rats, 4-week-old SD rats were divided into 10 groups randomly, according to their body weight. Rats in treatment groups were orally gavaged with BDE-99 at the dose of 60 mg kg^?1 for 10, 15, 20, 30 or 40 days, while rats in control group received equal volume of corn oil. Serum levels of thyroxine (FT4), triiodothyronine (FT3), and thyroid stimulating hormone (TSH) were measured by radioimmunoassay. Sections of thyroids were dyed with hematoxylin-eosin (HE) to detect any pathologically alterations. In BDE-99 treated groups, on day 10, changes in serum levels of FT4, FT3 and TSH were not found. On days 15 and 20, serum levels of FT4 and FT3 decreased, accompanied by increased levels of TSH. On days 30 and 40, serum levels of these hormones returned to control values. As for alterations in histology, on day 15, follicular epithelium of the thyroid were found to proliferate into two layers in BDE-99 treated rats. On day 20, in focal areas the two-layer follicular epithelia were observed to continuously proliferate into 3–4 layers of follicular epithelium, called hyperplasia plaques. On days 30 and 40, solid buds and secondary follicles to solid buds were detected. The earliest alteration of thyroid hormones in treated SD rats occurred at the duration of 10–15 days, with corresponding histopathologic changes. As the exposure time increased, the serum level of hormones and histopathology altered accordingly in a time-dependent manner.     

多溴二苯醚及其代谢物的内分泌干扰活性和构效关系研究进展

多溴二苯醚(Polybrominated diphenyl ethers,PBDEs)作为一种良好的防火溴系阻燃剂(Brominated flame retardants,BFRs)广泛应用于各种家用和工业产品.研究表明,PBDEs容易从产品中溢出而进入环境.近年来,PBDEs及其代谢物已在各种环境介质和生物体中被广泛检出.毒理学研究发现,PBDEs及其代谢物具有生殖毒性、免疫毒性、神经毒性和内分泌干扰作用.在总结国内外相关研究基础上,论文综述了PBDEs及其代谢物的内分泌干扰活性,重点集中在对甲状腺激素活性、雌激素活性、雄激素活性及影响性激素转化和代谢的芳香化酶、CYP17酶、雌二醇磺基转移酶(E2SULT)活性的影响;分析了具有不同测试终点内分泌干扰活性的化合物的结构特征.研究发现,在内分泌干扰活性方面,PBDEs母体化合物的影响较小,主要是PBDEs代谢物产生的影响,特别是羟基化代谢物引起了较严重的内分泌干扰作用,即PBDEs化合物是一类通过代谢而被活化的内分泌干扰前趋物.为评价PBDEs及其代谢物对人和其他生物的健康危害,应加强其内分泌干扰活性机制的研究,以及具有同类型作用模式的PBDEs及其代谢物定量结构-活性关系的研究.     

多溴联苯醚的生物富集效应研究进展

研究污染物的生物富集效应对于预测污染物在生物体内的含量、建立环境标准以及评估污染物的生态风险具有重要的意义.论文结合近年来国内外有关多溴联苯醚(PBDEs)的生物富集及其沿食物链(网)生物放大效应的研究文献,对PBDEs的生物富集效应进行了综述.文献计算的生物富集因子(BAFs)、生物-沉积物/土壤生物富集因子(BSAFs)和生物放大因子(BMFs)表明,生物对大多数PBDEs具有生物富集作用,且生物对PBDEs的富集能力与其生物进化等级及其营养级有关.文献计算的营养级放大因子(TMFs)表明,大多数PBDE单体可以在食物网上产生生物放大效应,但只有较少单体具有统计上的显著性.生物的生理生化参数、化合物本身的特性以及环境条件等因素影响了PBDEs在生物体内及食物链(网)上的富集与放大.     

十溴联苯醚（BDE-209）对成年大鼠甲状腺激素的影响

多溴联苯醚(PBDEs)是现代工业中广泛应用的溴系阻燃剂,PBDEs具有持久性有机卤素污染物(Organohalogen Contaminants,OHCs)和内分泌干扰物(Endocrine Disrupters,EDs)的化学物理特性.PBDEs的生物毒性也是国际上环境生态科学的关注热点.论文建立了十溴联苯醚(BDE-209)暴露剂量的成年大鼠模型,测定了不同暴露剂量的实验动物血清甲状腺激素(Thyroid hormones,THs)水平,初步研究了PBDEs污染物对生物体甲状腺激素的影响.BDE-209的量-效关系研究结果显示,TT4、FT4和TT3浓度均随着暴露剂量的提高而下降,这可能是BDE-209对甲状腺合成分泌T4、T3起到了抑制作用.不同BDE-209暴露剂量下,TT4~FT4以及TT4~TT3的正相关系数大于FT3~TT3以及FT3~FT4,这意味着BDE-209暴露对于T4从甲状腺激素转运结合蛋白(Transthyretin,TTR)的分离与脱碘过程影响不明显,而影响了结合态T3从TTR的分离过程以及FT4的脱碘过程,从而对甲状腺激素的平衡具有干扰效应.采用基准点分析法,研究了BDE-209对于甲状腺干扰相对效应的时间-效应关系,实验表明由于甲状腺的应激作用,对于毒物具有自我防御功能,BDE-209对甲状腺的干扰效应在5~8d后才有所显现,持续时间至少为14d.