多溴联苯醚的生物效应研究

多溴联苯醚(Polybrominated diphenyl ethers,PBDEs)由于其良好的阻燃性能被广泛应用于电子电器,家具,装饰材料及其他产品中。自使用以来,PBDEs在环境、生物体、人体中的污染水平快速增长,对生物体及人体的潜在危害日趋严重。国际社会已经认识到其危害性,部分PBDEs产品,如六溴联苯醚、七溴联苯醚、四溴联苯醚、五溴联苯醚已被列入禁用名单。文章概述PBDEs在生物体中的污染水平、生物累集效应以及PBDEs在生物体内的转化及代谢效应,着重阐述了PBDEs对神经系统、生物转化酶系统、抗氧化防御系统、生殖系统及内分泌系统的毒性效应,同时对PBDEs毒性作用机制及PBDEs环境相关污染浓度研究提出展望。     

多溴联苯醚环境行为对生态环境的研究进展

多溴联苯醚PBDEs(polybrominated diphenyl ethers)是一种常用的阻燃剂,已被纳入POPs(persistent organic pollutants)名单。本文综述了PBDEs的环境行为研究进展,以期为未来研究提供参考。     

MeO-PBDEs的来源、分布特征及分析方法研究进展

多溴联苯醚(PBDEs)是环境中广泛存在的一类持久性有机污染物,因其高残留性、高富集性以及对生态和人体健康的危害,被许多国家禁止使用。甲氧基多溴联苯醚(MeO-PBDEs)是PBDEs的主要衍生物之一,因其与PBDEs具有相似的结构、性质,引起了学者的广泛关注。文章简要介绍了MeO-PBDEs的性质、污染来源、在环境及生物体中的分布和检测方法,对近年来MeO-PBDEs研究的进展进行了综述,以期为中国开展MeO-PBDEs相关研究提供参考。     

羟基化多溴联苯醚(OH-PBDEs)在小鼠肝脏S9中的体外代谢研究

羟基化多溴联苯醚(OH-PBDEs)是一类具有内分泌干扰性质的酚类化合物,且内分泌干扰效应大于其母体多溴联苯醚(PBDEs),研究OH-PBDEs的体外代谢行为对于理解其在生物体内的富集转化具有重要意义.以小鼠肝脏S9部分作为研究对象,考察了3-OH-BDE-47、5-OHBDE-47、6-OH-BDE-47和2'-OH-BDE-68在小鼠肝脏中的体外代谢.结果表明小鼠肝脏S9中的I相酶和II相酶均能代谢4种OH-PBDEs;醚键与OH官能团及Br原子互为邻位时,I相酶对OH-PBDEs的代谢率最高,即6-OH-BDE-47表现出较高的代谢率,此外,4种OH-PBDEs经I相酶代谢后均能生成2,4-二溴苯酚,表明醚键断裂是其主要的I相酶代谢途径;OH-PBDEs的OH官能团与醚键互为间位时,II相酶对其葡萄糖醛酸结合反应最高,也就是5-OH-BDE-47表现出较高的去除率.     

中国地区多溴联苯醚在不同环境介质中的监测进展

多溴联苯醚(Polybrominated diphenyl ethers, PBDEs)为一类新型的溴代阻燃剂,广泛应用于塑料制品、纺织品、电路板和建筑材料等领域。随着生产量和使用量的增加,PBDEs已造成全球环境污染,其带来的环境问题已引起各国关注。同时PBDEs的长距离迁移性和难降解性,使其在环境介质中进行富集,从而加重污染。归纳了中国地区PBDEs的监测进展,分别从大气、水体、沉积物和土壤中PBDEs的污染水平以及原因进行了分析和探讨。在此基础上,对于我国PBDEs的研究方向提出了展望。     

垃圾焚烧发电厂周边土壤多溴联苯醚污染特征及来源解析

为了分析市政垃圾焚烧发电厂PBDEs(polybrominated diphenyl ethers,多溴联苯醚)排放对周边环境的影响,于2012年8—9月,在哈尔滨2座市政垃圾焚烧发电厂周边共采集20个表层(0~10 cm)土壤样品,分析土壤中PBDEs的污染特征及其来源. 结果表明:垃圾焚烧发电厂周边土壤中w(∑₁₂PBDEs)(12种PBDEs的质量分数之和)为5.32~169 ng/g(以干质量计,下同),平均值为62.9 ng/g;PBDEs的主要组分为BDE-209,w(BDE-209)为5.18~169 ng/g,占w(∑₁₂PBDEs)的95%以上;w(∑₁₂PBDEs)显著高于2006年哈尔滨市区污染土壤值,二者相差1~2个数量级. 由于垃圾处理年限和处理量差异较大,垃圾焚烧发电厂A周边土壤中w(PBDEs)显著高于垃圾焚烧发电厂B. 与国内其他用地类型污染土壤相比,垃圾焚烧发电厂周边土壤中PBDEs处于中度污染水平. 主成分分析结果显示,PBDEs主要来源于商用十溴联苯醚及其降解物和商用五溴联苯醚.      

一种新型环境污染物：羟基化多溴联苯醚（OH-PBDEs）

近年来羟基化多溴联苯醚（OH—PBDEs）在诸多环境介质中陆续被检出,其中一些被证明能在生物体内蓄积,另外一些被证明能产生致毒效应．作为一种新型的有机污染物,OH—PBDEs逐渐成为环境工作者研究的新热点．本文介绍了OH-PBDEs在环境中的来源及暴露水平,概述了国内外最近几年关于OH-PBDEs的环境浓度检测、生物体...     

4种典型羟基化多溴联苯醚对斑马鱼胚胎的毒性和生物富集性

羟基化多溴联苯醚(OH-PBDEs)是近年来发现的一种新型有机污染物,它的存在与人类生产的PBDEs有着密切的关系,因而备受关注.本文以斑马鱼胚胎为受试生物,研究了2'-羟基-2,3',4,5'-四溴联苯醚(2'-OH-BDE-68)、3-羟基-2,2',4,4'-四溴联苯醚(3-OH-BDE-47)、5-羟基-2,2',4,4'-四溴联苯醚(5-OH-BDE-47)、6-羟基-2,2',4,4'-四溴联苯醚(6-OH-BDE-47)4种典型OH-PBDEs对斑马鱼胚胎毒性效应和富集规律,测定了孵化率、存活率、正常率、心率、体长等指标和斑马鱼早期生活阶段体内的生物富集系数.结果表明,4种OH-PBDEs暴露引起斑马鱼胚胎孵化率、心率、存活率下降,畸形率升高并抑制生长发育.组织病理学研究显示,受试组斑马鱼与空白相比,出现鳃结构紊乱、腮丝上皮增厚、组织残损、脱落甚至坏死及脊椎变形等症状.2'-OH-BDE-68、3-OH-BDE-47、5-OH-BDE-47、6-OH-BDE-47的生物富集系数(45 d-BCF值)分别为424、244、588和144.     

中国大气环境中溴代阻燃剂污染特征研究进展

根据近年来大气环境中溴代阻燃剂(brominated flame retardants,BFRs)污染问题的研究成果,综述了溴代阻燃剂在中国大气环境中的污染特征。重点分析了多溴联苯醚(polybrominated diphenyl ethers,PBDEs)和部分Non-PBDE溴代阻燃剂(Non-PBDE类BFRs)在不同类型大气环境中的含量水平及分布特征。文献研究结果表明,中国的室内空气、电子垃圾拆解地、特殊工业园区和经济较发达城市大气环境PBDEs污染较严重,含量水平在102~103pg/m~3。中等发达地区城市大气中PBDEs含量处于世界中等水平,含量为10~102pg/m~3。最主要PBDEs同系物为BDE-209,其次是BDE-47、BDE-99和BDE-28。中国针对大气环境中Non-PBDE类BFRs污染问题的研究较少,现有结果表明,部分地区该类污染物的含量较高,达到103pg/m~3。主要的Non-PBDE类BFRs包括HBCDD、BTBPE及DBDPE。文章最后对中国大气环境中BFRs相关研究中存在的问题进行了简要的总结和展望。     

多溴联苯醚在电子废弃物拆卸地沉积物中的垂直分布

采用气相色谱质谱联用仪对采自清远电子废弃物拆卸地水库钻孔沉积物中的多溴联苯(polybrominated diphenyl ethers,PBDEs)进行了分析,调查其在沉积物中的垂直分布.结果表明,PBDEs在所有的样品中均检出,含量为0.43～141 ng/g,平均为9.26 ng/g.PBDEs在下层(16 cm以下)沉积物中含量较低、变化很小(0.43～2.30 ng/g),但在上层沉积物中含量明显增加(2.90～141 ng/g),反映了当地电子废弃物拆卸活动的影响;3种工业源的PBDEs,即五溴、八溴和十溴PBDEs,表现出相似的垂向分布趋势,说明其来源的一致性.其中,十溴PBDEs是最主要的PBDEs,平均占所有PBDEs的79.6%,其次是五溴PBDEs(14.7%),而八溴PBDEs所占比例最低(5.69%).3种PBDEs的组成模式显示,它们与相应的工业品PBDEs组成都有一定差异,可能因其降解行为不同所致.一些PBDE的同族体组成在沉积钻孔的垂直变化也进一步说明高溴代PBDE在沉积物的埋藏期间可能发生了降解,虽然还需要进一步研究证实.     

Transformation of hydroxylated and methoxylated 2,2′,4,4′,5-brominated diphenyl ether(BDE-99) in plants

The occurrence and fate of hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs) have received significant attention. However, there is limited information on the metabolism relationship between OH-pentaBDEs and MeO-pentaBDEs that were frequently detected with relatively high concentrations in the environment. In this study, the biotransformation between OH-BDE-99 and MeO-BDE-99 was investigated in rice, wheat, and soybean plants. All the three plants can metabolize OH-BDE-99 to corresponding homologous methoxylated metabolites, while the transformation from MeO-BDE-99 to OH-BDE-99 could only be found in soybean. The conversion of parent compounds was the highest in soybean, followed by wheat and rice. Transformation products were found mainly in the roots, with few metabolites being translocated to the shoots and solution after exposure. The results of this study provide valuable information for a better understanding of the accumulation and transformation of OH-PBDEs and MeO-PBDEs in different plants.     

羟基多溴联苯醚对鲤鱼急性毒性及定量结构活性关系

羟基多溴联苯醚是一类具有环境风险的新兴污染物,它们已经在众多环境介质甚至人体内广泛存在。参照GB/T13267-91标准方法,采用静态生物急性毒性试验,测定了6种羟基多溴联苯醚(2′-OH-BDE7、4′-OH-BDE17、2′-OH-BDE28、2′-OH-BDE68、4′-OH-BDE90和2′-OH-BDE123)对普通鲤鱼的急性毒性96 h-LC50值,分别为697、1 130、854、550、644和522 ng.mL-1。除4′-OH-BDE17为高毒物质外,其他5种OH-PBDEs均为剧毒物质,高溴代的2′-OH-BDE123毒性最大。选用OH-PBDEs的KOW参数及由MOPAC软件PM3算法计算出的16个量子化学参数(EHomo、qBr+、ELumo等)为描述符,运用一元线性回归分析分别研究了96 h-LC50与他们之间的相关关系。结果表明:lgKOW和ELumo与6种羟基多溴联苯醚的96 h-lg LC50表现出较好的相关性,复相关系数均大于0.96,根据方程得到的96 h-lg LC50预测值与实验值基本相同,进一步对环境中广泛检出的其它OH-PBDEs的96 h-LC50值也进行了预测。     

昆明市大气总悬浮颗粒物和PM2.5上多溴联苯醚的分布特征和潜在风险

为探究PBDEs（多溴联苯醚）在昆明大气中的环境行为,于2014年3月对昆明8个采样点大气TSP（总悬浮颗粒物）和PM_2.5样本进行了收集并利用GC-MS技术对其上附着的PBDEs的13种同系物进行了测定,进而对TSP和PM_2.5上PBDEs的分布特征和潜在风险进行了分析.结果表明:附着在TSP上的∑PBDE浓度（多溴联苯醚的总质量浓度）的范围为21.10~175.00 pg/m3.而附着在PM_2.5上的∑PBDE浓度范围为17.50~149.00 pg/m3,约占TSP中∑PBDE浓度的35.31%~85.14%,并且高溴化的同系物（BDE-138~BDE-209）比低溴化的同系物（BDE-17~BDE-99）更容易附着在PM_2.5上,约占∑PBDE浓度的8.50%~61.60%.对大气颗粒物中PBDEs的潜在影响和空气吸入暴露剂量评估结果表明,成人和儿童对PBDEs的DED_air（呼吸日暴露量）分别在5.28~43.75和6.90~57.23 pg/（kg·d）之间,TDI（每日总摄入量）分别在114.78~951.09和150.00~1 244.13 pg/（kg·d）之间,远低于最低无害水平[1 mg/（kg·d）].BDE-99的TDI分别为11.09~72.39和14.35~94.57 pg/（kg·d）,均低于最低摄入水平[260 pg/（kg·d）].研究显示,昆明市大气TSP和PM_2.5上的PBDEs对人体不存在健康风险.      

多溴联苯醚及其环境行为

多溴联苯醚(PBDEs)在环境中的浓度快速增长,在各种生物体和人体中也发现了PBDEs的存在,因此已经成为了全球性的环境污染物,是目前研究的一大热点。文章介绍了PBDEs的物理化学性质、分析方法、在环境中的分布归趋和控制措施,着重介绍了水环境中PBDEs的分布和归趋。     

Uptake, translocation, and debromination of polybrominated diphenyl ethers in maize

Uptake, translocation and debromination of three polybrominated diphenyl ethers (PBDEs), BDE-28, -47 and -99, in maize were studied in a hydroponic experiment. Roots took up most of the PBDEs in the culture solutions and more highly brominated PBDEs had a stronger uptake capability. PBDEs were detected in the stems and leaves of maize after exposure but rarely detected in the blank control plants. Furthermore, PBDE concentrations decreased from roots to stems and then to leaves, and a very clear decreasing gradient was found in segments upwards along the stem. These altogether provide substantiating evidence for the acropetal translocation of PBDEs in maize. More highly brominated PBDEs were translocated with more difficulty. Radial translocation of PBDEs from nodes to sheath inside maize was also observed. Both acropetal and radial translocations were enhanced at higher transpiration rates, suggesting that PBDE transport was probably driven by the transpiration stream. Debromination of PBDEs occurred in all parts of the maize, and debromination patterns of different parent PBDEs and in different parts of a plant were similar but with some differences. This study for the first time provides direct evidence for the acropetal translocation of PBDEs within plants, elucidates the process of PBDE transport and clarifies the debromination products of PBDEs in maize.     

Accumulation of polybrominated diphenyl ethers in breast milk of women from an e-waste recycling center in China

Polybrominated diphenyl ethers(PBDEs) can be transferred to infants through the ingestion of breast milk, resulting in potential health risk. In this study, PBDEs, hydroxylated polybrominated diphenyl ethers(OH-PBDEs) and 2,2′,4,4′,5,6′-hexachlorobiphenyl(CB-153)in human milk from women living adjacent to e-waste recycling sites of Wenling,China, were investigated. The median level of PBDEs in samples from residents living in the e-waste recycling environment 20 years(R_20group, 19.5 ng/g lipid weight(lw))was significantly higher than that for residents living in Wenling 3 years(R_3group,3.88 ng/g lw)(p 0.05), likely ascribable to specific exposure to PBDEs from e-waste recycling activities. In the R_20 group, most congeners(except for BDE-209) were correlated with each other(p 0.05). Moreover, CB-153 showed significant association with most PBDE congeners, rather than BDE-209. The relationship indicated that most BDE congeners other than BDE-209 shared common sources and/or pathways with CB-153, e.g., dietary ingestion. The correlations between BDE-209 and other congeners were different in the two groups, likely suggesting their different exposure sources and/or pathways for PBDEs.Although estimated dietary intake of PBDEs for infants via breast milk was lower than the minimum value affecting human health, the PBDE exposure of infants should be of great concern because of their potential effect on the development of neonates over long-term exposure. OH-PBDEs were not detected in the collected samples, which is in accordance with reports in published literature, likely indicating that they were not apt to be accumulated in human milk.     

加速溶剂萃取-气质联用同步测定土壤中17组分多溴二苯醚

建立了加速溶剂萃取-气相色谱-质谱法(ASE-GC/MS)同步定量分析土壤中17组分多溴二苯醚(PBDEs)的方法.选用正己烷和二氯甲烷混合液(体积比为1∶1)为萃取剂,样品经加速溶剂萃取后由氧化铝复合硅胶柱净化,气相色谱-负化学源-质谱法测定.结果表明:在32 min内,包括高溴代二苯醚在内的17组分PBDEs同族体在同一较短毛细管色谱柱上得到了较好的分离.该方法中BDE209的回收率为80.80%,其余BDE的回收率为86.39%～103.19%;BDE209的方法检出限为198.33 pg/g,其他16组分PBDEs同族体的方法检出限为0.85～114.33 pg/g.该方法检测土壤中多组分PBDEs的灵敏度高、重现性和回收率良好,可用于土壤样品PBDEs的分析.      

Ecotoxicological effects of mixed pollutants resulted from e-wastes recycling and bioaccumulation of polybrominated diphenyl ethers in Chinese loach (Misgurnus anguillicaudatus)

To understand potential ecotoxicological effects of electrical and electronic equipment waste (e-waste) recycling and polybrominated diphenyl ethers (PBDEs) bioaccumulation in loaches, a semi-field experiment using Chinese loach (Misgurnus anguillicaudatus) as experimental fish was performed. Larval loaches were kept into net-cage for three months in an e-wastes recycling site and a reference site in Southeastern China. There was significant difference of the survival rate between the loaches from the e-wastes recycling site (27%, 19/70) and from reference site (70%, 49/70). Histopathological responses were also found in all the livers examined in loaches from the e-wastes recycling site. These results showed that mixed pollutants resulted from e-wastes recycling led to ecotoxicological effects on loaches. The bioaccumulation of polybrominated diphenyl ethers (PBDEs), the main pollutants in e-waste, in loaches was also studied in this e-wastes recycling site, the mean concentrations of total PBDEs in sediment was 6726.17 ng/g wet weight and in water samples was 4.08 ng/L (dissolved phase). BDE209 was the dominant congener in sediment and with relatively high concentration in water. Relatively low concentration of BDE209 (less than 0.01% of total PBDEs) and high concentration of BDE47 (up to 39.34% of total PBDEs) were detected in loaches.     

环境中多溴联苯醚污染状况调查及其对人体健康的影响研究

多溴联苯醚（ PBDEs ）作为阻燃剂在日常生活中被广泛应用。 PBDEs是一种新增的环境持久性有机污染物,在环境中不易降解,且具有亲脂性、生物富集性和生物毒性,并能通过多种传输途径在全球范围内迁移,所造成的环境问题已成为目前环境科学研究的热点。针对该问题,综述了近些年环境中PBDEs的污染研究进展,分析空气、水与日常食物中PBDEs的污染水平,对人体PBDEs暴露的途径以及环境中PBDEs污染对人类健康产生的影响进行了总结。并且对目前存在的问题以及进一步的研究方向进行讨论和展望,提出应加强对环境中PBDEs污染的调查研究,开展人体PBDEs暴露的潜在风险评估,为保证居民健康提供科学依据。     

微生物降解多溴联苯醚研究进展

多溴联苯醚(PBDEs)广泛用于电子电器设备、自动控制设备、建筑材料和纺织品等商品化产品中。作为工业阻燃剂,它是一类环境中广泛存在的全球性有机污染物。由于其结构稳定,难以降解,具有环境持久性、迁移性、生物富集性及对生物和人体具有毒害效应等特性,对其微生物降解的研究已成为当前生命科学的新兴热点。文章详细地探讨了国内国外微生物厌氧,有氧降解PBDEs以及其降解基因的最新研究进展,并针对目前的研究状况对今后PBDEs的微生物降解研究方向进行了展望。