微波萃取-气相色谱/质谱测定底泥中多溴联苯醚

文章建立微波萃取,复合硅胶氧化铝层析柱净化,气相色谱-负化学离子源质谱(GC-NCI-MS)检测对环境底泥样品中七种多溴联苯醚(PBDEs)单体定量分析的方法。底泥样品经25 mL正己烷:丙酮(1:1)萃取剂微波萃取10 min,过复合层析柱净化,70 mL正己烷:二氯甲烷(1:1)洗脱和浓缩后,加入内标物PCB-103后进行内标定量分析,7种PBDEs单体的平均基质加标回收率均值为88.6%~96.7%,相对标准偏差为1.9%~9.3%,方法检出限均小于0.06 ng/g,方法具有良好的重现性,较好的回收率和较高的灵敏度。所建立的分析方法体系已用于长江口近岸沉积物中7种PBDEs残留量的检测,四个实际样品中添加回收率指示物PCB-209,其回收率范围为79.5%~109.6%,相对标准偏差为5.2%~16.5%。     

海洋生物样品中多溴联苯醚和多溴联苯的分析研究

将气相色谱-负离子化学源／质谱法(GC-NCI/MS)应用于分析海洋生物中五种多溴联苯醚(PBDEs)和五种多溴联苯(PBBs)残留.样品以正己烷／丙酮(1:l,v/v)作为提取剂,采用超声萃取法,提取液经酸性硅胶和中性硅胶层析柱净化和正己烷洗脱后,以PCB-103为内标物和GC-NCI/M的选择离子监测方式(SIM)...     

环渤海沉积物中多溴联苯醚(PBDEs)的研究

采用同位紊稀释高分辨气相色谱-质谱法,对环渤海海域的16个表层沉积物样品中的PBDEs进行了研究.研究结果表明环渤海区域ΣPBDEs含量水平差异较大,西部海域污染较其它区域严重.但与世界其它地区相比,总体的含量水平较低,与中国南海北部海域以及韩国近海海域基本相当.沉积物中PBDEs的污染模式以BDE209为主,反映了十溴联苯醚是我国目前使用最多的溴代阻燃剂.     

四川妇女血清中多溴联苯醚的浓度水平与组成特征

用气相色谱-质谱的选择离子法测定四川省妇女血清中多溴联苯醚的质量浓度,并对其组成特征及主要来源进行了研究.在被测的11种多溴联苯醚当中,BDE-209是主要成分,质量浓度从0.12～2.38μg.L-1,中值为0.63μg.L-1,占多溴联苯醚总量的质量分数为63.57%～90.34%,其次是BDE-66、-99和-100,其它多溴联苯醚几乎没有检出,表明污染主要来自十溴联苯醚,其次是四溴和五溴联苯醚.实验结果与其它国家的数据相比,表明多溴联苯醚对普通妇女的污染在四川还处于一个较低的水平.     

污水及污泥中多溴联苯醚的研究进展

多溴联苯醚是一类溴代阻燃剂,包括三种主要的工业产品,五溴、八溴、十溴联苯醚.该物质曾广泛使用于电子、材料、家具等产品中.研究表明,在这些产品的生产、使用和处理过程中均会释放多溴联苯醚到周边环境中.多溴联苯醚具有持久性、可生物富集和长距离迁移,对人体和身体系统存在潜在危害,是一类新兴污染物.目前,这类物质中的部分化合物已...     

多溴联苯醚降解技术的研究进展

多溴联苯醚(PBDEs)是一类环境中广泛存在的全球性有机污染物。由于其环境持久性、毒性和潜在的生物蓄积性而备受关注,如何处理环境中的PBDEs已成为当前研究的热点问题之一。该文综述了国内外对PBDEs不同处理方法的最新研究进展,重点探讨了生物降解和光降解两大方面进展,并对目前存在问题及进一步的研究方向进行了展望。     

多溴联苯醚好氧生物降解研究

研究了好氧真菌白腐菌对4, 4′-二溴联苯醚（BDE15）和十溴联苯醚(BDE209)的降解,并考察了不同浓度Tween　80和β-环糊精的加入对BDE15和BDE209表观溶解度和生物降解的影响.结果表明,白腐菌对BDE209和BDE15均有显著降解作用,培养10　d后,BDE209的降解率达到43.0％,降解了约69.7　μg,BDE15则由150　μg降至4.8　μg,扣除其挥发损失,降解率达62.5％.低浓度Tween　80(≤700 mg/L)和β-环糊精对白腐菌降解BDE209均有明显的促进作用,而高浓度的Tween　80（900 mg/L）则会抑制白腐菌生长,从而抑制其降解作用.Tween 80和β-环糊精（500 mg/L）对BDE15的降解均有一定抑制作用.Tween　80和β-环糊精对BDE209降解的促进作用主要是由于其对BDE209的增溶作用,对BDE15的抑制作用可能是由于Tween　80胶束和β-环糊精空腔对BDE15的包裹降低了水中可直接利用的自由态BDE15,影响了降解速度.     

环境样品中多溴联苯醚的分析技术综述

随着众多环境样品中多溴联苯醚(PBDEs)的检出,以及这种物质持久性污染的性质,它正在引起人们的持续关注,对这类物质的分析检测也随之增多,本文侧重于对分析技术的各个环节中不同选择的优缺进行分析,包括样品预处理及提取、进样工艺、色谱分离、质谱检测等环节,通过对比,得出不同实验环境下更为合适的分析工艺。     

固相萃取-气相色谱法测定水中13种多溴联苯醚

建立水中13种多溴联苯醚(Polybrominated diphenyl ethers,PBDEs)固相(solid-phase extraction,SPE)萃取-气相色谱分析方法。水样经弗罗里硅土(Florisil)固相萃取柱富集后,用2 mL正己烷和5 mL正己烷:二氯甲烷(V∶V=8∶2)进行洗脱,采用HP-5(30 m×320μm×0.25μm)毛细管柱分离,气相色谱仪(GC-uECD)检测。结果表明,在0.05、0.25、0.5μg/L3个添加水平中,13种PBDEs的平均添加回收率在67.9%~121.5%的范围内,相对标准偏差为2.5%~12.3%。其中BDE-209的平均添加回收率为67.9%~71.9%,相对标准偏差为5.2%~8.0%。BDE-209的方法检出限是1.2 ng/L;其余12种PBDEs的方法检出限是0.11~0.5 ng/L。该方法准确度较高;稳定性和回收率良好;可测定多组分PBDEs,满足环境样品中PBDEs的分析。     

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。     

珠江三角洲地区男性血液中多溴联苯醚暴露水平与精液质量的研究

采集了珠江三角洲地区103名成年男性的血液和精液样本,运用冷冻干燥-ASE萃取-GC-MS方法测定了血液中多溴联苯醚(PBDEs)含量,并按照WHO的精子质量检测标准及仪器操作规范检测精液质量,分析了血液中PBDEs与男性精液质量之间的相关性,同时,探讨了不同因素与血液中PBDEs含量之间的关系.结果表明,不同年龄对血液中PBDEs含量的影响未呈现一致的趋势,除BDE-47外,不同体重指数(BMI)人群组单个PBDEs含量差异不显著,吸烟者血液中PBDEs含量高于不吸烟者,饮酒者和不饮酒者则与之相反,随着学历升高,PBDEs含量水平未有递增或递减的一致规律;BDE-153、BDE-154和BDE-183含量与精液浓度显著负相关,而PBDEs与精子活动性不相关.因此,血液中PBDEs含量与珠江三角洲地区男性精液质量无显著相关性.     

Occurrence of polybrominated diphenyl ethers in fish and shellfish downstream from electronic-waste recycling plants

We measured 39 polybrominated diphenyl ethers (PBDEs) in the muscle tissue of three species of fish (Sciaenops ocellatus, Sparus macrocephalus, and Lateolabrax japonicus) and four species of shellfish (Tegillarca granosa, Cyclina sinensis, Sinonovacula constricta, and Ostrea cucullata) that were collected downstream of electronic-waste recycling plants in Taizhou, China. A total of 24 PBDE congeners (PBDE24) in the samples were detected. The PPBDE24 (total PBDE) ranged from 545.4 to 1688.7 ng/kg ww (wet weight). The mean PPBDE24 concentration was 1382.6 ng/kg ww in fish and 858.1 ng/kg ww in shellfish. The lower brominated congeners were detected at relatively high concentrations in all species. The penta-products, produced from e-waste, were found at relatively low levels. A principal component analysis suggested a significant correlation among di-, tri-, tetra-, and hepta-BDEs for the three species of fish. Similarly, we found a significant correlation between mono- and tri-BDEs in the shellfish. Our results suggested that the processes of PBDE metabolism and elimination were similar in both fish and shellfish. In addition, the primary source of PBDEs appeared to be from the debromination of high brominated PBDEs.     

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.     

莱州湾地区土壤及底泥中多溴联苯醚水平及其分布

对莱州湾地区十溴联苯醚生产厂家附近土壤及底泥中的多溴联苯醚的含量进行了检测.所采集土壤和河流底泥样品中Σ8 PBDEs(BDE-28、-47、-100、-99、-154、-153、-183、-209) 的含量在58.2～7190.7 ng·g-1(干重)之间, 所有样品中,BDE-209 相对含量最高,其对Σ8PBDEs 的贡献为74.81% ～99.01 %.在8种PBDEs同族体的相关性研究中发现BDE-209与BDE-183、-154、-153、-100、-99呈现显著负相关,相关系数r为-0.842～-0.996(α=0.01).BDE-183、-154、-153、-100、-99之间呈显著正相关,相关系数r为0.805～0.994(α=0.01).产品十溴联苯醚在环境中的降解可能是测定样品中BDE-99、-100、-153、-154、-183的来源之一.     

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.     

珠江三角洲沉积物钻孔中多溴联苯醚的垂直变化规律研究

采用GC/MS分析方法测定了珠江三角洲水体5个钻孔(分别采自东江东莞段、珠江广州段、北江中段、西江入海口和顺德段)80个样品中10种多溴联苯醚(PBDEs,BDE209和∑9BDEs)的含量,对其沉积规律进行研究和探讨.∑9BDEs含量范围为1.54~94.8 ng·g-1,平均值为15.4 ng·g-1.BDE209含量范围为14.4~588 ng·g-1,平均值为136 ng·g-1,占总PBDEs含量的70%以上.钻孔中PBDEs含量从底部到表层呈现上升趋势,表明近年来珠江三角洲PBDEs环境排放仍在增加.5个钻孔中低溴代∑9BDEs从表层至底部逐渐增加,而高溴代∑9BDEs逐渐减少,意味着钻孔中可能存在脱溴降解行为.     

Distribution of polybrominated diphenyl ethers and decabromodiphenylethane in surface sediments from Fuhe River and Baiyangdian Lake, North China

Nineteen surface sediment samples collected from Baiyangdian Lake and its inflowing river (Fuhe River) in North China were analyzed for polybrominated diphenyl ethers (PBDEs) and decabromodiphenylethane (DBDPE). The concentrations of PBDEs and DBDPE in sediments ranged from 5.5 to 300.7 ng/g dry weight (dw) and 1.1 to 68.2 ng/g dw, respectively. Their levels in sediments in Fuhe River were significantly higher than those in Baiyandian Lake. Compared to data from other regions, the PBDE levels in surface sediments from Baiyangdian Lake and Fuhe River were in the medium to lower range. Among the PBDE congeners, BDE209 was predominant, with contributions to the total PBDEs ranging from 79.4% to 97.3% in sediment samples. For the lowly brominated congeners (tri- to hepta-BDE), BDE47 and BDE99 were the most abundant, which contributed 52.1% and 44.1% to the sum of tri- to hepta-BDEs in the sediments from Baiyangdian Lake and Fuhe River, respectively. The compositional patterns of PBDEs in Baiyangdian Lake sediments indicated that technical deca-BDE mixture was the major pollutant sources with a minor contribution of penta-BDE mixture. The present study suggested that the importance of Fuhe River as a possibly potential sources of PBDEs contamination in Baiyangdian Lake.     

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.     

A review of polybrominated diphenyl ethers and alternative brominated flame retardants in wildlife from China: Levels, trends, and bioaccumulation characteristics

Accelerated industrialization and urbanization, and unregulated disposal of waste of electric and electronic equipment (e-waste) in China have caused environmental pollution of brominated flame retardants (BFRs). This review summarized the levels, trends, and bioaccumulation characteristics of polybrominated diphenyl ethers (PBDEs) and other potential alternative BFRs including hexabromocyclododecanes (HBCDs), 1,2-bis(2,4,6-dibromophenoxy) ethane (BTBPE) and decabromodiphenylethane (DBDPE) in wildlife from China. PBDE levels in wildlife from China were generally higher than those from other parts in Asia, and were comparable to those from Europe but were lower than those from North America. However, wildlife from the e-waste recycling sites in South China and East China contained much higher PBDEs compared to other reports around the world, suggesting the heavy contamination of PBDEs in these regions. The alternative BFRs were also detected in wildlife, revealing that the animals are exposed to these chemicals, in addition to PBDEs. Temporal trends indicated by levels in marine mammals from South China suggested that PBDE levels increased from the beginning of 1990s to 2000s, but decreased from the middle of 2000s, followed by relatively steady levels. In contrast, HBCDs were found to be continuously increasing from 1997 to 2007, indicating the increasing usage of HBCDs in China in recent years. Compared to PBDE profiles found in other parts, aquatic species and birds from China contained relatively higher contributions of BDE-28 and 209, respectively, suggesting the possible different usage pattern of PBDEs. Future works including keeping monitoring at a reasonable scale and frequency to make sure levels near urban centers indicative of population do not increase are needed. Additionally, focus effort on e-waste recycling regions to look for impacts and to determine if regulation/controls are resulting in lower environmental contamination, and incorporation of sentinel species in monitoring efforts are recommended.