An international survey of decabromodiphenyl ethane (deBDethane) and decabromodiphenyl ether (decaBDE) in sewage sludge samples

Decabromodiphenyl ethane (deBDethane) is an additive flame retardant marketed as a replacement for decabromodiphenyl ether (decaBDE). The structures of the two chemicals are similar, and hence deBDethane may also become an environmental contaminant of concern. Environmental data on deBDethane are scarce. Since sewage sludge is an early indicator of leakage of these chemicals into the environment, an international survey of deBDethane and decaBDE levels in sludge was conducted. Samples were collected from 42 WWTPs in 12 different countries and analyzed with GC/LRMS. DeBDethane was present in sludge from all countries and may therefore be a worldwide concern. The levels of deBDethane in sludge samples from the Ruhr area of Germany were the highest so far reported in the literature (216 ng g⁻¹ d.wt.). The [deBDethane]/[decaBDE] quotient for the whole data set ranged from 0.0018 to 0.83. High ratios were found in and around Germany where deBDethane imports are known to have been high and substitution of decaBDE with deBDethane is likely to have occurred. Low ratios were found in the USA and the UK, countries that have traditionally been large users of decaBDE. An estimate of the flux of deBDEthane from the technosphere via WWTPs to the environment within the European Union gave 1.7 ± 0.34 mg annually per person. The corresponding value for decaBDE was 41 ± 22 mg annually per person.     

十溴二苯乙烷对蚯蚓亚急性毒性及微生物群落结构影响

新型溴系阻燃剂十溴二苯乙烷(DBDPE)生产和使用量日益增大,在环境中的检出率越来越高,其生态风险正受到广泛关注.然而,有关DBDPE对陆地无脊椎生物毒性效应以及微生物群落结构的影响知之甚少.探究了不同剂量(5、10、20、50和100mg·kg-1)DBDPE暴露对赤子爱胜蚓(Eisenia fetida)生长、行为...     

十溴二苯乙烷对部分血糖内分泌干扰的计算机辅助理论研究

随着十溴二苯乙烷(decabromodiphenyl ethane,DBDPE)的大量应用,它已经广泛存在于各种环境介质中,具有潜在的生物毒性。为了探究DBDPE影响血糖代谢水平的具体作用机制,应用DS3.5软件将其与部分血糖内分泌蛋白受体进行分子对接,并利用DBDPE类似物来构建三维定量构效关系(3D-QSAR)模型,预测出DBDPE的半最大效应浓度的负对数值(-log EC50)为5.86。结果表明,DBDPE是通过与部分血糖内分泌受体(雌激素受体、甲状腺激素受体和孕激素受体)结合而影响血糖代谢水平的。另外,根据构建模型,可以预测类似DBDPE的未知内分泌干扰物的活性数据。这些为认识DBDPE在机体内的作用机制、全面评价它的生态风险提供了理论依据。     

土壤中十溴二苯乙烷(DBDPE)的植物吸收传输特征及微观机制研究

采用温室土培实验,研究了土壤中新型溴代阻燃剂十溴二苯乙烷（DBDPE）在不同种属植物中的吸收和传输特征,以及植物脂的影响作用;进一步应用计算模拟的手段解析了植物载脂蛋白与DBDPE的分子间相互作用,以阐明DBDPE的植物吸收传输的微观机制.结果表明,在玉米、小麦和黄瓜3种植物的根和地上部均检测到了DBDPE,根中DBDPE的含量高出地上部1~2个数量级.植物中累积的DBDPE量随时间的变化存在明显的生长稀释效应（p<0.05）.DBDPE的根吸收和茎向传输表现出植物种属间的显著差异（p<0.05）,根富集因子（RCF）顺序为黄瓜（0.30~0.57） > 小麦（0.10~0.39） > 玉米（0.03~0.26）,而传输系数（TF）为小麦（0.17~0.20） > 玉米（0.16~0.19） > 黄瓜（0.04~0.07）.DBDPE的根吸收量及RCF值与植物根脂含量成显著正相关关系（r=0.94,p<0.01;r=0.98,p<0.01）;其地上部累积量及TF值与植物地上部脂含量显著正相关（r=0.77,p<0.05;r=0.94,p<0.05）,但与植物根脂含量呈显著负相关关系（r=-0.74,p<0.05;r=-0.76,p<0.05）,说明脂是控制植物吸收和传输DBDPE的重要组分.分子对接的结果显示,DBDPE能键合进入3种植物载脂蛋白的活性区域并与载脂蛋白特异性的活性位点作用,且DBDPE与载脂蛋白的结合方式及结合能力存在植物种属的显著差异,两者的结合强弱与根吸收DBDPE能力的顺序一致,印证了实验结果.本研究有助于理解植物中DBDPE的吸收传输特征及机制,可为深入认识DBDPE的陆生生态环境行为提供重要依据.     

生物炭负载零价纳米铁去除土壤中十溴二苯乙烷

作为十溴联苯醚的替代品,新型溴代阻燃剂十溴二苯乙烷（DBDPE）已经在国内外大量使用.随着DBDPE在各种环境介质中被普遍检测到,其造成的环境污染正引起广泛关注.本论文首先制备生物炭（BC）负载零价纳米铁（nZVI）材料（BC/nZVI）,进而研究了BC/nZVI去除土壤中DBDPE的动力学过程,并探究了作用机制.结果表明：BC加入能促进nZVI均匀分散在生物炭的表面,并改善了其分散程度;BC/nZVI去除效率最高（投加量为0.1 g·g^-1,BC：nZVI为2：1,DBDPE初始浓度为10 mg·kg^-1）,24 h内达到了89.74%,去除过程涉及到吸附和降解的共同作用,实验数据符合准一级动力学方程;采用LC-MS-MS探究了DBDPE的降解产物和途径;ECOSAR毒性评价数据显示BC/nZVI能够降低DBDPE的生态毒性.     

环境样品中三种新型溴代阻燃剂的分析测定

采用索氏抽提、多层硅胶氧化铝柱分离净化和气相色谱质谱联用仪(GC-EI-MS和GC-ECNI-MS)分别对沉积物及土壤样品中的十溴二苯基乙烷(DBDPE),四溴舣酚A双(2,3-二溴烯丙基)醚(TBBPA-DB-PE),1,2-双(2,4,6-三溴苯氧基)乙烷(BTBPE)3种新型溴代阻燃剂进行了定性和定量分析,并建立了环境样品中这3种新型溴代阻燃剂的检测方法.在3个流程空白中,所有目标物都低于检出限;加标空白中日标化合物DBDPE,TBBPA-DBPE,BTBPE的回收率分别为74.8%-82.5%,88.9%-100.7%,86.7%-102.3%.方法检出限分别为1ng·g~(-1),0.4ng·g~(-1)和0.1ng·g~(-1).DBDPE,TBBPA-DBPE,BTBPE在沉积物和土壤样品中测定结果的相对标准偏差分别为16.29%,0.045%,0.051%.方法具有较低的方法检出限,较好的回收率和重复性,适用于一般环境样品中新型溴代阻燃剂的分析和检测.     

Conventional and emerging halogenated flame retardants (HFRs) in sediment of Yangtze River Delta (YRD) region,East China

The occurrence and distribution of polybrominated diphenyl ethers (PBDEs) and eleven non-PBDE halogenated flame retardants (HFRs) were investigated through the collection of marine and river sediment from Yangtze River Delta (YRD), East China. Among them, PBDEs, decabromodiphenyl ethane (DBDPE) and 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) were the three predominant HFRs with the highest detection frequencies in the sediment. Significant correlation between PBDEs and DBDPE indicated that they may have the similar emission sources. The production and use of DBDPE is growing rapidly and comparable concentrations between PBDEs and DBDPE in YRD sediment may suggest that DBDPE will likely become one of the major HFRs emerging in the environment in China. Of the seven detected non-PBDE HFRs, this is the first time that TBECH was reported in the Chinese environment and its predominance and prevalence in the YRD may imply its extensive use in these areas.     

Photolytic degradation of decabromodiphenyl ethane (DBDPE)

The photolytic degradation of decabromodiphenyl ethane (DBDPE), an alternative flame retardant to decabromodiphenyl ether, was investigated in a variety of matrixes (n-hexane, tetrahydrofuran, methanol/water, humic acid/water, and silica gel) by irradiation under ultraviolet light and in n-hexane under natural light. Photolytic degradation of DBDPE occurs in all the matrixes investigated within the irradiation period (<320 min). The degradation experiments showed varied reaction rates, dependent on the matrixes, with increasing half-lives (t_1/2) in the order of tetrahydrofuran (t_1/2 = 6.0 min) > n-hexane (t_1/2 = 16.6 min) > humic acid/water (30 < t_1/2 < 60) > silica gel (t_1/2 = 75.9 min) > methanol/water (t_1/2 > 240 min). The reaction in tetrahydrofuran, n-hexane, and silica gel matrixes can be described by the pseudo first order kinetics. Nevertheless, the matrixes have little effect on the degradation product distributions of DBDPE. A numbers of debrominated intermediates were identified. The degradation involves the initial formation of nona-BDPEs and the subsequent decomposition of these congeners to lower brominated congeners (octa- and hepta-BDPEs) within the irradiation time. To our knowledge, the present work is the first attempt to investigate the photolytic degradation kinetics and the identification of intermediates, as well as the degradation mechanism, during the degradation of DBDPE. Further research is needed to understand the photolytic degradation pattern of DBDPE in the natural environment.     

十溴二苯乙烷阻燃聚合物材料的性能评价研究

分析了十溴二苯醚(DBDPO)在环保方面受限的趋势以及十溴二苯乙烷(DBDPE)作为替代品所具有的优势。用DBDPE制得的各种阻燃材料(PP、ABS、HIPS)与DBDPO相应制得的阻燃材料进行对比分析,结果显示DBDPE制品各种参数随添加剂的变化趋势比DBDPO制品缓慢,但总体上DBDPE与DBDPO制品的性能比较接近甚至更好,DBDPE可替代DBDPO应用在阻燃材料中。