2,4,4'-三溴联苯醚的光降解研究

以固相微萃取(SPME)结合气相色谱(GC)、气相色谱-质谱联用(GC/MS)技术作为分析检测手段,研究光源、有机溶剂、无机盐与腐殖酸对BDE-28光降解的影响,实验结果表明,光源是影响其降解的主要因素,其次,丙酮、铜离子和腐殖酸对其降解的影响较显著.光源对BDE-28光降解速率的影响为300 W汞灯500 W金卤灯100 W汞灯500 W氙灯;有机溶剂对BDE-28降解速率的影响为甲醇/水(1∶1)甲醇己烷甲苯乙腈丙酮;无机离子的影响各有差别:K+、Na+、SO2-4、NO-3、Cl-对BDE-28降解影响不明显,而Fe3+、NH+4促进BDE-28的降解,Fe2+、Cu2+、Br-抑制BDE-28的降解;腐殖酸抑制BDE-28的降解.     

沉积物中不同浓度多壁碳纳米管对Cd和BDE-47生态毒性的影响

随着碳纳米管的广泛应用,其将不可避免地进入环境中.由于其具有极好的吸附亲和力和吸附容量,碳纳米管可以充当环境中持久性有毒污染物的载体,从而改变共存污染物的生物有效性和生态毒性.为评价淡水沉积物中不同多壁碳纳米管(MWCNTs)对Cd和BDE-47生态毒性的影响,采用沉积物慢性生物测试研究了不同浓度MWCNTs存在下Cd和BDE-47对铜锈环棱螺肝胰脏抗氧化防御系统关键成分超氧化物歧化酶(SOD)与Ⅱ相解毒反应的关键酶谷胱甘肽-S-转移酶(GST)以及脂质过氧化损伤指标丙二醛(MDA)的影响.结果表明,沉积物中低浓度MWCNTs(0.5 mg·g~(-1))增强Cd对铜锈环棱螺的氧化胁迫,中、高浓度(5、50 mg·g~(-1))MWCNTs引起Cd对铜锈环棱螺的氧化损伤,MWCNTs的存在显著增强了沉积物中Cd对铜锈环棱螺的毒性,而且具有浓度-效应关系;低浓度MWCNTs不影响BDE-47对铜锈环棱螺的毒性,中、高浓度MWCNTs显著降低BDE-47的毒性,同样具有明显的浓度-效应关系.因此,在评价MWCNTs的潜在环境风险时,不仅考虑MWCNTs自身的毒性,还应当考虑MWCNTs的浓度、共存污染物的种类和MWCNTs与共存污染物之间的相互作用.     

Effects of two polybrominated diphenyl ethers (BDE-47, BDE-209) on the swimming behavior,population growth and reproduction of the rotifer Brachionus plicatilis

Polybrominated diphenyl ethers(PBDEs) are new kinds of persistent organic pollutants(POPs) and their potential threats to the equilibrium and sustainability of marine ecosystems have raised worldwide concerns. Here, two kinds of PBDEs, tetra-BDE(BDE-47)and deca-BDE(BDE-209) were applied, and their toxic effects on the swimming behavior,population growth and reproduction of Brachionus plicatilis were investigated. The results showed that:(1) The actual concentrations of BDE-47 and-209 in the seawater phase measured by GC–MS(Gas Chromatography-Mass Spectrometer) were much lower than their nominal concentrations.(2) In accordance with the 24-hr acute tests, BDE-209 did not show any obvious swimming inhibition to rotifers, but a good correlation did exist between the swimming inhibition rate and BDE-47 concentration suggesting that BDE-47 is more toxic than BDE-209.(3) Both BDE-47 and-209 had a significant influence on the population growth and reproduction parameters of B. plicatilis including the population growth rate, the ratio of ovigerous females/non-ovigerous females(OF/NOF), the ratio of mictic females/amictic females(MF/AF), resting egg production and the mictic rate, which indicate that these parameters in B. plicatilis population were suitable for monitoring and assessing PBDEs. Our results suggest that BDE-47 and-209 are not acute lethal toxicants and may pose a low risk to marine rotifers at environmental concentrations for short-term exposure. They also accumulate differently into rotifers. Further research data are needed to understand the mechanisms responsible for the effects caused by PBDEs and to assess their risks accurately.     

Effects of two polybrominated diphenyl ethers (BDE-47, BDE-209) on the swimming behavior, population growth and reproduction of the rotifer Brachionus plicatilis

Polybrominated diphenyl ethers (PBDEs) are new kinds of persistent organic pollutants (POPs) and their potential threats to the equilibrium and sustainability of marine ecosystems have raised worldwide concerns. Here, two kinds of PBDEs, tetra-BDE (BDE-47) and deca-BDE (BDE-209) were applied, and their toxic effects on the swimming behavior, population growth and reproduction of Brachionus plicatilis were investigated. The results showed that: (1) The actual concentrations of BDE-47 and -209 in the seawater phase measured by GC-MS (Gas Chromatography-Mass Spectrometer) were much lower than their nominal concentrations. (2) In accordance with the 24-hr acute tests, BDE-209 did not show any obvious swimming inhibition to rotifers, but a good correlation did exist between the swimming inhibition rate and BDE-47 concentration suggesting that BDE-47 ismore toxic than BDE-209. (3) Both BDE-47 and -209 had a significant influence on the population growth and reproduction parameters of B. plicatilis including the population growth rate, the ratio of ovigerous females/non-ovigerous females (OF/NOF), the ratio of mictic females/amictic females (MF/AF), resting egg production and the mictic rate, which indicate that these parameters in B. plicatilis population were suitable for monitoring and assessing PBDEs. Our results suggest that BDE-47 and -209 are not acute lethal toxicants and may pose a low risk to marine rotifers at environmental concentrations for short-term exposure. They also accumulate differently into rotifers. Further research data are needed to understand the mechanisms responsible for the effects caused by PBDEs and to assess their risks accurately.     

2,2’,4,4’—四溴联苯醚对2种赤潮微藻种间竞争的影响

基于Logistic种群增长模型,研究了2,2’,4,4’—四溴联苯醚(BDE-47)的亚急性毒性胁迫对不同初始接种生物量比的赤潮异弯藻(Heterosigmaakashiwo)和米氏凯伦藻(Kareniamikimotoi)种间作用的影响.结果发现:不同的初始接种生物量比影响微藻间的竞争.加入0.05、0.25 mg/LBDE-47后,对于K. mikimotoi而言,不同初始生物量比的处理组表现出高浓度组的最大环境容纳量、种群瞬时增长率均大于低浓度组(P<0.05),而H. akashiwo高浓度组的最大环境容纳量、种群瞬时增长率均小于低浓度组(P<0.05).微藻之间的竞争表现出向着对K. mikimotoi有益方向发展的规律,因此一定浓度下的BDE-47干扰了两种微藻之间的竞争.     

典型电器工业区河涌沉积物中的多溴联苯醚空间和垂直分布

对珠江三角洲佛山市顺德区容桂镇电器工业区河涌沉积物多溴联苯醚(PBDEs)的含量进行了空间和垂直分布研究.选择该镇中心城区内河涌作为研究河道,根据河涌水流情况选取8个采样点采集沉积物样品.所有样品中均检出PBDEs.各监测点的PBDEs总含量变化范围为62～349 ng.g-1(平均为178 ng.g-1),各采样点的浓度差异较大.其中,十溴联苯醚含量为56～337 ng.g-1(平均为171 ng.g-1),占PBDEs总含量的90%～99%(平均95%).所检测到的部分同系物(如BDE-196、197和203)可能是BDE-209的降解产物.PBDEs的垂直分布模式显示,0～10 cm层面样品的PBDEs浓度为147 ng.g-1,30～40 cm层面样品的PBDEs浓度为260 ng.g-1,PBDEs在沉积物中的丰度随垂直深度的增加而增加.12种同系物在采自各个深度层样品中的比例基本相同,由十溴工业品来源的BDE-209、208、207和206占总PBDEs的94%,而五溴和八溴所占比例较低.由此可见,该地区普遍存在PBDEs污染,其中十溴联苯醚是最主要污染物,这可能与十溴工业品是电器工业主要使用的阻燃材料相关.     

十溴联苯醚的热解及其影响因素研究

在200~300℃的温度范围内研究了十溴联苯醚(BDE-209)的热降解及其影响因素.结果表明,温度、时间以及硝酸铜、三氯化铁、氯化铝和氯化锌等处理线路板过程中产生的金属盐对BDE-209热降解有不同的影响.升高温度或延长热解时间均能促进BDE-209的热解,且温度对BDE-209降解的影响程度大于时间对其降解的影响;硝酸铜、三氯化铁和氯化铝对BDE-209的热解均起促进作用,促进作用的顺序为:硝酸铜 >三氯化铁 >氯化铝;氯化锌对BDE-209的热解有抑制作用;随着温度的升高,氯化铝和氯化锌对BDE-209热降解的影响减弱.该研究结果可为深入探究电子垃圾热处理过程中BDE-209的释放及降解提供科学依据.     

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.     

四溴联苯醚(BDE-47)对两种海洋桡足类动物的毒性效应

为了研究四溴联苯醚(BDE-47)对海洋桡足类的毒性效应,以太平洋真宽水蚤和日本虎斑猛水蚤为受试生物,依据急性毒性实验96 h-LC₅₀值,设置5个浓度组和1个对照组,测定摄食率、滤水率、耗氧率、排氨率和抗氧化防御系统中SOD、GST、GPx活性以及GSH含量。结果显示：BDE-47对太平洋真宽水蚤和日本虎斑猛水蚤的96 h-LC₅₀分别为
57和851 μg·L^-1,后者明显高于前者。2种桡足类在BDE-47作用下,其能量摄入和代谢均受到不同程度的诱导或抑制。太平洋真宽水蚤在中浓度(1.425 μg·L^-1)下摄食率和排氨率受到促进,高浓度(5.70和11.40 μg·L^-1)下耗氧率明显抑制;日本虎斑猛水蚤高浓度下(170.20 μg·L^-1)摄食率受到抑制,中浓度(21.28 μg·L^-1)下耗氧率受到促进,各个浓度的BDE-47对其排氨率均有明显促进作用。太平洋真宽水蚤SOD活性在BDE-47暴露96 h过程中均低于对照组(P<0.05),受到明显抑制;GST活性随暴露时间延长先升高后降低;GSH含量和GPx活性低浓度(0.7125和1.425 μg·L^-1)下随时间先升高后降低,而高浓度(5.70和11.40 μg·L^-1)下则相反。日本虎斑猛水蚤SOD活性随BDE-47浓度的升高先降低后升高再降低;GST活性和GSH含量在低浓度(10.64和21.28 μg·L^-1)BDE-47中与对照组相比无显著差异(P>0.05),而高浓度(85.10和170.20 μg·L^-1)
BDE-47下,GST活性随时间先升高后降低,GSH含量则先降低后升高再降低;GPx活性呈现先降低后升高趋势。由此可见,BDE-47与这2种桡足类的能量摄入、代谢和抗氧化防御系统存在一定时间及剂量效应,并具有明显的物种差异性。     

BDE-47对斑马鱼胚胎-幼鱼的急性毒性及氧化应激作用

为研究2,2',4,4'-四溴联苯醚(BDE-47)对斑马鱼胚胎-幼鱼急性毒性、氧化应激及细胞凋亡的影响,以受精后3 h的斑马鱼胚胎为染毒对象,用概率单位法计算BDE-47对斑马鱼胚胎-幼鱼的96 h-LC₅₀;再参照96 h-LC₅₀按一定比例级差设置0.25、0.5、1.0、2.0 mg·L^-1 4个浓度组和1个对照组(0 mg·L^-1)进行96 h半静水式毒性试验,检测斑马鱼超氧化物歧化酶(SOD)及过氧化氢酶(CAT)活性、丙二醛(MDA)含量和细胞凋亡情况。结果表明,BDE-47对斑马鱼96 h的急性毒性LC₅₀为3.77 mg·L^-1(95%可信区间1.93～10.27 mg·L^-1);2.0 mg·L^-1剂量组与对照组相比,SOD活性和MDA含量显著增加,且CAT活性与BDE-47染毒浓度之间存在明显的剂量-效应关系;0.5 mg·L^-1 BDE-47染毒96 h后,即观察到斑马鱼幼鱼出现明显细胞凋亡,主要集中于神经管和脑部。研究表明,BDE-47可以影响斑马鱼体内抗氧化防御系统,并能诱导细胞凋亡;BDE-47导致神经组织的氧化损伤可能在动物神经毒性中起重要作用。