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。     

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。     

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1 440.67 ng·g-1(以样品于质量计).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,摄人速率常数、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(160 ng· g-1)暴露对铜锈环棱螺的潜在繁殖力没有影响,但当浓度≥640 ng·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。     

丙硫菌唑对斑马鱼的安全性评价及其生物富集行为研究

丙硫菌唑是一种市场前景非常好的新型广谱杀菌剂。本文研究了丙硫菌唑对水生生物斑马鱼的急性毒性和生物累积风险。通过斑马鱼的急性毒性试验获得丙硫菌唑对斑马鱼的96 h-LC₅₀为2.06 mg a.i. L^-1。随后,采用0.02 mg L^-1 (1/100LC₅₀)和0.2 mg L^-1 (1/10LC₅₀)2个浓度的丙硫菌唑,通过8 d实验,获得其在斑马鱼体内的生物累积效应。在0.02 mg L^-1组中,第8天时,斑马鱼体内的浓度达到0.733 mg kg^-1,生物富集系数(BCF_{8 d})缓慢增长到34.36。而在0.2 mg L^-1组,第8天时,斑马鱼组织内丙硫菌唑浓度为4.198 mg kg^-1, BCF_{8 d}值为19.72。结果表明,丙硫菌唑对斑马鱼的毒性等级为中毒,同时其在斑马鱼体内具有中等生物累积效应。因此,在使用过程中,需要考虑其对水生生物的毒性和水生食物链的放大效应。     

啶氧菌酯对斑马鱼的安全性评价及其生物富集行为研究

啶氧菌酯是一种新型的内吸性杀菌剂,本研究对其水生生物的毒性和累积风险进行了评估。啶氧菌酯原药对斑马鱼的急性毒性试验结果显示,96 h-LC₅₀为0.0509 mg a.i. L^-1。设置0.005 mg L^-1(1/100LC₅₀)和0.05 mg L^-1(1/10LC₅₀)2个浓度8 d生物累积试验。在0.005 mg L^-1组,第8天斑马鱼体内啶氧菌酯浓度达到0.48 mg kg^-1,生物富集系数(BCF_{8 d})缓慢增长到80.00。而在0.05 mg L^-1组,第8天斑马鱼体内的啶氧菌酯浓度为5.27 mg kg^-1,BCF_{8 d}值为99.42。研究表明,啶氧菌酯对斑马鱼为有剧毒,同时具有中等生物累积效应。因此在使用过程中,需要考虑其对水生生物的毒性和水生食物链的放大效应。     

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。     

PFOS潜在替代品全氟丁基磺酸钾对不同营养水平水生生物的毒性

全氟丁基磺酸钾(PFBSK)作为全氟辛基磺酸(PFOS)潜在的替代品,极易溶于水,主要存在于水体中,因而其水生毒性的研究十分重要。采用OECD 201、OECD 202、OECD 203和OECD 211标准试验方法,研究了PFBSK对羊角月牙藻(Pseudokirchneriella subcapitata)、大型溞(Daphnia magna)和中国本土鱼种稀有鮈鲫(Gobiocypris rarus)的急性毒性效应以及对大型溞繁殖的影响。组合多终点急慢性水生生物毒性结果：PFBSK的急性毒性终点均大于100 mg·L^-1,大型溞繁殖试验的无观察效应浓度(NOEC)为571 mg·L^-1,最低可观察效应浓度(LOEC)为981 mg·L^-1。按GHS分类导则,PFBSK未表现出急性毒性和慢性毒性。与之相比,PFOS则对水生生物表现出毒性,黑头软口鲦(Pimephales promelas)为最敏感物种,其96 h-LC₅₀为4.7 mg·L^-1;大型溞繁殖试验的NOEC为12 mg·L^-1。按GHS分类导则,属于中等毒性物质。可见,PFBSK较PFOS水生毒性明显降低。     

不同土壤类型中外源汞对白符跳（Folsomia candida）的毒性研究

参考国际标准化组织(ISO)颁布的跳虫毒性测试方法 ISO11267,分析了汞(Hg)在我国9种典型土壤中对白符跳(Folsomia candida)的急性毒性及繁殖毒性。发现Hg在不同类型土壤中对白符跳的半数致死浓度(LC₅₀)变化为(0.92～1.94) mg·kg^-1,而对白符跳繁殖产生影响的半数效应浓度(EC₅₀)变化范围为(0.98～2.43) mg·kg^-1,产生10%影响的浓度(EC10)变化范围为(0.29～1.40) mg·kg^-1 。将土壤的主要理化性质(pH、OM、CEC)与Hg对白符跳的EC₅₀进行相关性回归分析,发现土壤CEC与EC₅₀呈显著正相关关系(r=0.8624,p<0.01),随着土壤CEC的增大,Hg的EC₅₀值也趋于升高。因此,土壤CEC可能是导致不同类型土壤中汞对白符跳毒性差异的主要因素。本研究结果可为制定基于我国土壤类型的生态筛选值提供基础参考数据。     

卤代有机化合物生物富集因子的定量结构-活性关系模型

依据经济合作与发展组织(OECD)关于定量结构-活性关系(QSAR)模型构建和使用导则,通过多元线性回归(MLR)方法建立了一个包含9个描述符的卤代有机化合物鱼类生物富集因子(BCF)的QSAR模型。QSAR模型的调整决定系数R²_adj = 0.877,去一法交叉验证系数Q²_LOO= 0.873,外部验证系数Q²_EXT= 0.757,表明模型具有较好的拟合优度、稳健性和预测能力。采用欧几里德距离方法表征了模型应用域,并对模型进行了机理解释。所构建的模型,可以用于预测应用域内卤代化合物的BCF。     

Occurrence and profiles of polybrominated diphenyl ethers (PBDEs) in riverine sediments of Shanghai: a combinative study with human serum from the locals

Herein, we studied the occurrence and profiles of thirteen PBDE congeners in 30 river sediment samples from Shanghai, China. The concentrations of Σ₁₃PBDEs ranged from 110 to 13,071 pg g ^?1 dw, with an average value of 2,841 pg g ^?1 dw. BDE-209 was the predominant congener accounting for more than 65 % of total PBDEs, demonstrating that the major source of PBDEs in sediment samples was associated with the prevalent use of technical deca-BDE products. Moreover, low brominated BDEs in sediments also came from the degradation of higher brominated BDEs. In addition, taking into consideration of dietary exposure, PBDEs in serum samples collected from the locals were also detected with range of 419–26,744 pg g^?1 (average 5,561 pg g ^?1), which suggested a relatively low burden of PBDEs contamination to human body compared with the condition in other place. And in serum, low brominated compounds constituted the majority of total PBDE congeners.     

Increasing polybrominated diphenyl ether (PBDE) contamination in sediment cores from the inner Clyde Estuary,UK

The concentrations of 16 polybrominated diphenyl ether (PBDE) congeners in six short sediment cores from the Clyde Estuary were determined by gas-chromatography mass-spectrometry. Total PBDE concentrations ranged from 1 to 2,645 μg/kg and the average concentration was 287 μg/kg. BDE-209 was the main congener and varied from 1 to 2,337 μg/kg. Elevated total PBDE concentrations were observed close to the sediment surface in the uppermost 10 cm of four of the six sediment cores. Comparison of the down core PBDE profiles revealed that the increase was driven by the accumulation of deca-BDE. Although the deca-BDE mix was dominant, the presence of lower molecular weight congeners BDE-47, BDE-99, BDE-183 and BDE-153 at most sediment intervals suggested additional sources of penta-BDE and octa-BDE pollution. Changing PBDE source input was the major factor in influencing the proportion of nona-brominated congeners, although other explanations such as post burial photo-debromination of BDE-209 cannot be entirely discounted. A clear cascading to lower hepta-, hexa-, and penta-homologues was not found. The increase in total PBDE concentrations and particularly the deca-BDE may possibly be ascribed to the use and subsequent disposal of electrical appliances such as televisions and computers. In the Clyde sediments, the proportion of nona-brominated congeners was higher than that reported for commercial mixtures. This might be due to changing sources of PBDEs or post burial photo-debromination of BDE-209.     

Removal of decabromodiphenyl ether (BDE-209) by sepiolite-supported nanoscale zerovalent iron

Nanoscale zerovalent iron (nZVI) synthesized using sepiolite as a supporter was used to investigate the removal kinetics and mechanisms of decabromodiphenyl ether (BDE-209). BDE-209 was rapidly removed by the prepared sepiolite-supported nZVI with a reaction rate that was 5 times greater than that of the conventionally prepared nZVI because of its high surface area and reactivity. The degradation of BDE-209 occurred in a stepwise debromination manner, which followed pseudo-first-order kinetics. The removal efficiency of BDE-209 increased with increasing dosage of sepiolite-supported nZVI particles and decreasing pH, and the efficiency decreased with increasing initial BDE-209 concentrations. The presence of tetrahydrofuran (THF) as a cosolvent at certain volume fractions in water influenced the degradation rate of sepiolite-supported nZVI. Debromination pathways of BDE-209 with sepiolite-supported nZVI were proposed based on the identified reaction intermediates, which ranged from nona- to mono-brominated diphenylethers (BDEs) under acidic conditions and nona- to penta-BDEs under alkaline conditions. Adsorption on sepiolite-supported nZVI particles also played a role in the removal of BDE-209. Our findings indicate that the particles have potential applications in removing environmental pollutants, such as halogenated organic contaminants.     

BDE-47和BDE-209对乙酰胆碱酯酶(AChE)活性的抑制特性及分子作用力研究

多溴联苯醚(PBDEs)是应用广泛的溴代阻燃剂,其中2,2',4,4'-四溴联苯醚(BDE-47)和2,2',3,3',4,4',5,5',6,6'-十溴联苯醚(BDE-209)广泛存在于环境中。PBDEs具有神经毒性,但其致毒机制尚不明确。本文通过研究BDE-47与BDE-209对乙酰胆碱酯酶(AChE)活性的影响及二者与AChE相互作用的光谱分析,揭示BDE-47与BDE-209导致神经毒性的致毒机制。BDE-47和BDE-209在一定浓度范围内均能够抑制AChE分解乙酰胆碱;随着浓度的增加,两者的抑制率均呈现出先增加后降低的规律。BDE-47浓度为400μmol·L-1时抑制率达到最大,为22.3%;BDE-209浓度为200μmol·L-1时抑制率达到最大,为11.2%。相同浓度下,BDE-47对AChE的抑制率始终大于BDE-209,表明AChE对BDE-47更加敏感。荧光光谱分析结果表明BDE-47和BDE-209与AChE之间的相互作用均主要为疏水作用,同时不存在范德华引力作用;BDE-47与AChE的结合常数大于BDE-209与AChE的结合常数,表明BDE-47更易与AChE相互作用。此外,温度的升高不利于BDE-47和BDE-209与AChE之间相互作用。BDE-47和BDE-209抑制AChE活性很可能是导致神经毒性通路之一。     

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。     

十溴联苯醚(BDE-209)对离体条件下小鼠肾脏和脑组织SOD活力和MDA含量的影响

十溴联苯醚(decabromodiphenyl ether,BDE-209)是目前应用最广泛的的溴系阻燃剂,其环境风险引起很大关注。本实验以小鼠肾脏和脑组织为实验材料,研究了离体条件下BDE-209的急性氧化损伤效应。BDE-209染毒终浓度设置为0,1,2,4和8μg·mL-1,采用NBT和TBA法分别测定SOD(superoxide dismutase)活性和MDA(malondialdehyde)含量。结果显示,随着BDE-209染毒浓度的升高,小鼠肾脏和脑组织的SOD活性先升高后降低,较高染毒浓度组的SOD活性与对照组相比显著性降低;MDA含量逐渐上升,并且与对照组相比较高染毒浓度组的MDA含量显著上升。以上结果说明,离体条件下BDE-209对小鼠肾脏和脑组织能够产生急性氧化应激,并导致脂质过氧化损伤。     

氟对中华圆田螺肝胰脏抗氧化酶活性和MDA含量的影响

选取中华圆田螺为受试动物,探究氟对其肝胰脏抗氧化酶SOD、GSH、POD活性和丙二醛(MDA)含量的影响。结果显示,在不同浓度水氟环境条件下(0、40、80、160 mg·L~(-1))连续暴露10 d、20 d和30 d时,与对照组相比,中华圆田螺肝胰脏SOD活性在暴露前20 d,中低浓度组活性被诱导升高,高浓度组受抑制降低。暴露30 d时,中低浓度组活性降低,高浓度组逐渐升高。MDA含量在暴露前20 d时,中低浓度组活性整体被诱导升高,高浓度组受抑制降低。暴露30 d时,MDA含量受到显著抑制均低于对照组。GSH活性以诱导为主均高于对照组,POD活性在10 d时均低于对照组,而在20 d时被诱导升高且均高于对照组,30 d时中高浓度以抑制为主。上述研究结果为水质污染控制及生态风险评价提供了基础数据。     

白腐菌对十溴联苯醚的酶促降解研究

考察了白腐菌菌体、胞外酶、胞内酶对十溴联苯醚(BDE-209)的降解性能,结果表明,白腐菌菌体、胞外酶、胞内酶对浓度为1 mg.L-1的BDE-209的降解率分别为60.17%、54.14%、22.32%,白腐菌对BDE-209的降解主要由胞外酶完成.进一步考察了温度、pH、BDE-209浓度对白腐菌胞外酶降解BDE-209的影响,结果显示,胞外酶降解BDE-209的最适条件为温度30℃、pH 4—5、BDE-209浓度1 mg.L-1.白腐菌胞外酶降解BDE-209前后红外光谱测定结果证实,BDE-209降解过程与Br—C、CH2—O—CH2等基团有关.降解后体系GC-MS谱图显示,BDE-209降解过程中存在脱Br作用.     

Polybrominated diphenyl ethers (PBDEs) in soil and dust from plastic production and surrounding areas in eastern of China

Polybrominated diphenyl ethers (PBDEs) are a class of organic pollutants. They are used as flame retardants that caused worldwide environmental concern. This study investigated the occurrence of PBDEs in soils and dusts from three plastic manufacture plants and surrounding areas in Eastern China. A total of 13 PBDE congeners were detected using gas chromatography-mass spectrometer (electron impact ionization). The total concentrations of PBDEs range from 2.21 to 558, 19.7–4916, and 8.70–18,451 ng/g dry weight in the soils of three sampling areas, with mean of 1004 ng/g d w; in dusts, the concentrations range from 7240 to 10,469, 684–4482, and 193–3989 ng/g d w, with an overall mean of 3619 ng/g d w. The most abundant congener is the BDE-209, followed by BDE-153 and BDE-85. This indicates that the brominated flame retardant added in the plastic manufacture is mainly the commodity decabromodiphenyl ether. In comparison with other polluted areas around the world, the PBDE concentrations in the soils of the plastic manufacture plants are similar to those in soils of waste plastic disposal areas and PBDEs production sites, but orders of magnitude higher than those in agricultural soils, mountain soils and rural soils. Daily exposure was estimated using the average concentrations of the pollution sites. The hazard quotient shows that the PBDEs pose considerable human health risks, especially to children, to which attention should be paid.