南海北部大气气相多溴联苯醚的含量及来源

通过"实验三号"开放航次在南海北部采集了32个大气样品,用气相色谱/质谱联用仪分析了样品中的多溴联苯醚(PBDEs)同系物,并对其含量、组成特征、空间分布及主要来源进行了研究.结果表明,南海北部大气中7种PBDEs总浓度为0.07～35.9 pg.m-3,四溴(BDE-47)和五溴(BDE-99和-100)化合物为主要组成,分别约占PBDEs总量的51.5%和36.9%,显示工业五溴联苯醚的使用是其主要来源;中国东南沿海和菲律宾附近PBDEs浓度较高,南海靠近越南中部海域大气PBDEs含量较低.后推气流轨迹分析指出:我国东南沿海,特别是珠江三角洲,以及我国台湾和菲律宾等地区陆源污染物的外溢是引起南海北部地区PBDEs浓度较高的主要原因.     

Debromination of decabromodiphenyl ether by organo-montmorillonite-supported nanoscale zero-valent iron：Preparation, characterization and influence factors

An organo-montmorillonite-supported nanoscale zero-valent iron material(M-NZVI) was synthesized to degrade decabromodiphenyl ether(BDE-209). The results showed that nanoscale zero-valent iron had good dispersion on organo-montmorillonite and was present as a core-shell structure with a particle size range of nanoscale iron between 30–90 nm, characterized by XRD, SEM, TEM, XRF, ICP-AES, and XPS. The results of the degradation of BDE-209 by M-NZVI showed that the efficiency of M-NZVI in removing BDE-209 was much higher than that of NZVI. The efficiency of M-NZVI in removing BDE-209 decreased as the pH and the initial dissolved oxygen content of the reaction solution increased, but increased as the proportion of water in the reaction solution increased.     

Enhanced debromination of 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) by zero-valent zinc with ascorbic acid

• Highly efficient debromination of BDE-47 was achieved in the ZVZ/AA system. • BDE-47 debromination by the ZVZ/AA can be applied to a wide range of pH. • AA inhibits the formation of (hydr)oxide and accelerates the corrosion of ZVZ. • Reduction mechanism of BDE-47 debromination by the ZVZ/AA system was proposed. A new technique of zero-valent zinc coupled with ascorbic acid (ZVZ/AA) was developed and applied to debrominate the 2,2′,4,4′-Tetrabromodiphenyl ether (BDE-47), which achieved high conversion and rapid debromination of BDE-47 to less- or non-toxic forms. The reaction conditions were optimized by the addition of 100 mg/L ZVZ particles and 3 mmol/L AA at original solution pH= 4.00 using the solvent of methanol/H₂O (v:v= 4:6), which could convert approximately 94% of 5 mg/L BDE-47 into lower-brominated diphenyl ethers within a 90 min at the ZVZ/AA system. The high debromination of BDE-47 was mainly attributed to the effect of AA that inhibits the formation of Zn(II)(hydr)oxide passivation layers and promotes the corrosion of ZVZ, which leads to increase the reactivity of ZVZ. Additionally, ion chromatography and gas chromatography mass spectrometry analyses revealed that bromine ion and lower-debromination diphenyl ethers formed during the reduction of BDE-47. Furthermore, based on the generation of the intermediates products, and its concentration changes over time, it was proposed that the dominant pathway for conversion of BDE-47 was sequential debromination and the final products were diphenyl ethers. These results suggested that the ZVZ/AA system has the potential for highly efficient debromination of BDE-47 from wastewater.     

Sorption kinetic characteristics of polybrominated diphenyl ethers on natural soils

Sorption kinetic characteristics of BDE-28 and BDE-47 on five natural soils with different organic carbon fractions were investigated, and could be satisfactorily described by a two (fast and slow)-compartment first-order model with the ratio of rate constants ranged from 9 to 94 times. The fast compartment made a dominant contribution (71% ∼ 94%) to the total sorption amount in the whole process, and accounted for over 90% of the increase in the total sorption amount at initial 5 h. The influence of the slow compartment on the increase in the total sorption amount became principal (above 90%) in the subsequent stage approximately from 9 h or 25 h to the apparent equilibrium at 265 h. The results proposed the different sorption behaviors of the mathematically classified compartments for BDE-28 and BDE-47, which may correspond to the different soil components, such as soil organic fractions with amorphous and condensed structures, respectively.     

Important role of reaction field in photodegradation of deca-bromodiphenyl ether: Theoretical and experimental investigations of solvent effects

Photolysis of deca-bromodiphenyl ether (BDE-209) was investigated in tetrahydrofuran, dichloromethane, isopropanol, acetone, ethanol, methanol, acetonitrile and dimethylsulfoxide. Noticeable differences of the photolytic rates and quantum yields were found in the diverse solvents. Different to the previous deductions, hydrogen donating efficiency and electron donating efficiency of solvents were not the decisive factors for the photolytic rate in this study, which was proved by the fast photolysis of BDE-209 in CCl₄, a solvent without hydrogen and difficult to donate electrons. Besides hydrogen addition process, intermolecular polymerization might occur during the photolysis. Density functional theory (DFT) calculation was performed to understand the molecular properties of BDE-209 in different solvents. The lowest singlet vertical excitation energy (E_ex) and the average formal charge on Br () of BDE-209, reflecting the difficulty for the excitation of BDE-209 and for the departing of Br atom, respectively, were changed by the reaction fields formed by the different solvents. E_ex and linearly correlated with the photolytic activity (log k). This study is helpful to better understand the photolytic behavior of BDE-209 in different media.     

Mechanism of Deca-BDE-induced apoptosis in Neuro-2a cells: Role of death-receptor pathway and reactive oxygen species-mediated mitochondrial pathway

Decabromodiphenyl ether (BDE-209) is a prevalent polybrominated diphenyl ether (PBDE) congener known to have neurotoxicity. Effects of BDE-209 on Neuro-2a cells were performed in the present study and the possible apoptotic pathway was discussed. Results indicated that BDE-209 induced Neuro-2a cell apoptosis, increased the protein expression of Fas and Fas-associated death domain-containing protein (FADD) and activated the caspase-8 and -3 activities in a concentration-dependent manner, inferring the death-receptor pathway was involved in the apoptotic process. Meanwhile, BDE-209 exposure increased the Bax/Bcl-2 ratio and decreased the cellular mitochondrial membrane potential (MMP) which led to cytochrome C released to the cytoplasm. The intracellular caspase-9 was elevated simultaneously, which caused downstream caspase cascade and triggered cell apoptosis. Moreover, BDE-209 exposure increased cellular reactive oxygen species (ROS) level in a concentration-dependent manner and the addition of N-acetyl-l-cysteine (NAC), known as ROS scavengers, obviously reduced the apoptotic rate and a positive relationship was observed between the degree of apoptosis blocking and the loss of MMP and ROS production. We thus concluded that BDE-209 induced Neuro-2a cell apoptosis via the combination of the death-receptor signaling pathway and the mitochondrial signaling pathway. The elevated ROS production was considered to magnify the intracellular apoptosis signal and played a crucial role in apoptosis of Neuro-2a cells induced by BDE-209.     

十溴联苯醚在单次暴露的孕和非孕SD大鼠血液内的吸收分布

五溴联苯醚、八溴联苯醚被禁以后,十溴联苯醚（BDE-209〉97%）是现在唯一仍在全球范围内广泛使用的多溴联苯醚阻燃剂。BDE-209在环境介质和生物体,甚至人体的血液、母乳中普遍存在,而且BDE-209的环境含量呈上升趋势。在实验室条件下,BDE-209可以通过生物代谢,或光降解、热降解转换形成毒性更强的低溴代PBDEs、羟基甲氧基PBDEs、致癌物多溴二苯并二噁英/呋喃（PBDD/DFs）。所以BDE-209的环境行为及生物效应成为环境污染物领域研究的热点之一。目前,关于BDE-209对妊娠期生物体的暴露研究还是很少。研究了十溴联苯醚在单次暴露的孕和非孕SD大鼠血液内的吸收代谢。结果表明,BDE-209可以被孕和非孕SD大鼠吸收,孕和非孕SD大鼠血液中吸收的BDE-209都可以快速的排出。BDE209在孕和非孕SD大鼠体内存在脱溴代谢,主要的脱溴代谢物是3种nona-BDE（sBDE-206,-207,-208）和五种octa-BDEs（BDE-196,-197/204,-198/203）,其中3种nona-BDEs是主要的代谢物,而BDE-207是nona-BDEs中含量最大的单体。BDE-209及其脱溴代谢物nona-BDEs的清除速率,在SD孕鼠的体内快于SD非孕鼠,而且在暴露实验的后期还存在统计意义的显著差异性。     

十溴联苯醚(BDE-209)对土壤跳虫的急、慢性毒性效应

为揭示溴代阻燃剂对土壤生态系统的潜在危害,采用回避实验和繁殖实验评价了十溴联苯醚(BDE-209)对2种土壤跳虫Folsomia candida和Folsomia fimetaria的急/慢性毒性。48h的急性回避实验中,BDE-209对F.candida和F.fimetaria产生毒性效应的EC_(50)值分别为1.27和0.79mg·kg~(-1),LOEC值均小于0.5mg·kg~(-1)。慢性繁殖实验中,BDE-209对F.candida和F.fimetaria繁殖毒性的EC_(50)值分别为0.81和0.56mg·kg~(-1),LOEC值分别为<0.25和<0.5mg·kg~(-1)。研究表明,土壤BDE-209污染对跳虫的繁殖和环境行为有显著影响,且在较低暴露浓度下(0.25mg·kg~(-1))即对跳虫繁殖产生抑制效应;有性生殖的F.fimetaria比孤雌生殖的F.candida对BDE-209污染的毒性响应更为敏感。     

沉积物中2,2',4,4'-四溴联苯醚(BDE-47)在铜锈环棱螺体内的毒代动力学及其繁殖毒性

多溴联苯醚(PBDEs)是一种全球性的新型持久性有毒污染物,沉积物中高浓度的PBDEs是水生态系统的巨大风险源,2,2’,4,4’-四溴联苯醚(BDE-47)在PBDEs同系物中,目前分布最广,生物毒性最强。为评价沉积物中BDE-47向底栖动物体内转移的潜力及其对底栖动物的潜在繁殖毒性,将实验室培养的铜锈环棱螺(Bellamya aeruginosa)暴露于BDE-47加标沉积物中,研究了BDE-47在铜锈环棱螺体内的毒代动力学特性及其对铜锈环棱螺潜在繁殖力的影响。结果表明,铜锈环棱螺对沉积物中BDE-47吸收较快,代谢速度相对较慢,BDE-47在铜锈环棱螺体内具有较强的生物积累性。生物积累达理论平衡时,铜锈环棱螺体内BDE-47浓度为1440.67ng·g-1(以样品干质量计)。BDE-47在铜锈环棱螺体内的生物积累和生物净化过程较好地符合一级动力学模型,摄入速率常数、清除速率常数和生物-沉积物累积因子分别为0.10、0.038和2.75,生物半衰期为18d。铜锈环棱螺体内BDE-47达到90%稳定状态所需的理论时间约为60d。低浓度BDE-47(160ng·g-1)暴露对铜锈环棱螺的潜在繁殖力没有影响,但当浓度≥640ng·g-1时,铜锈环棱螺的繁殖力下降50%,这表明BDE-47对铜锈环棱螺具有繁殖毒性。铜锈环棱螺可作为指示沉积物中底栖生物长期暴露于BDE-47的良好检测模型。     

BDE-47对2种海洋微藻光合特性的影响

研究了不同浓度的2,2′,4,4′-四溴联苯醚(BDE-47)对2种海洋微藻的光合特性的影响. 结果表明, 在试验所设定的浓度范围内 (0.1~2.5μg/L),海水小球藻和赤潮异弯藻的PSII最大光能转化效率(Fv/Fm)、光化学淬灭系数(qP)未受到显著抑制,表明2种微藻PSII反应中心在试验过程中未受到损伤.当BDE-47浓度为2.5μg/L时,海水小球藻的PSII潜在活性(Fv/Fo)、PSII实际光能转化效率(φPSII)和光合电子传递效率(ETR)在96h受到显著抑制,而赤潮异湾藻的3个参数在暴露期间均未受到抑制,表明赤潮异湾藻对BDE-47的耐受性强于海水小球藻.各叶绿素荧光参数中, Fv/Fo、φPSII、ETR更适合作为指示海洋环境中BDE-47污染水平的生物标志物.