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鲤鱼对羟基多溴联苯醚的生物富集行为研究
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摘要
羟基多溴联苯醚(OH-PBDEs)是近年来备受关注的一类新兴有机污染物,目前已在众多环境介质甚至人体内频繁检出,且具有很强的生物毒害效应。为了更好地评价OH-PBDEs的生态风险和最终归趋,本文研究了其在水生生物鲤鱼体内的富集行为,并探讨了生物富集效应的作用机理。
     首先,在前人研究的基础上,优化建立了鲤鱼肝脏、肾脏、脑及肌肉不同组织生物样品和自然水样中OH-PBDEs的分析方法。结果表明,OH-PBDEs同类物的加标回收率为62.6-118.2%,水样和生物样品的方法检测限分别为0.35-10.13ng/g(脂重)、4.2-85.0pg/mL,且方法重现性较好。
     然后,参照GB/T13267-91静态生物急性毒性实验标准方法,测定了OH-PBDEs同类物(2'-OH-BDE7、4'-OH-BDE17、2'-OH-BDE28、2'-OH-BDE68、4'-OH-BDE90和2'-OH-BDE123)对鲤鱼的96h-LC50值,分别为697、1130、854、550、644和522ng/mL选用OH-PBDEs同类物的Kow及量子化学参数(EHomo、qBr+、ELumo等)为分子结构描述符,分别研究了其与96h-LC50之间的相关关系。结果表明:lgKOW和ELumo与96h-lgLC50均具有良好的线性相关性,且96h-lgLC50预测值与实验值基本相同。
     最后,采用OECD及GB/T21800-2008标准方法,应用半静态双箱模型室内模拟鲤鱼对OH-PBDEs同类物(2'-OH-BDE68和4'-OH-BDE90)的生物富集实验,研究了其在肝脏、肾脏、脑及肌肉各组织中的富集和分布规律。结果表明:
     (1)鲤鱼各组织对2'-OH-BDE68和4'-OH-BDE90的富集与清除均遵循一级反应动力学规律;蓄积能力强,生物富集系数BCF(L/Kg)分别为1.4×102~8.0×103、35~2.2×103;吸收速率常数K1(d-1)大,分别高达357.1、49.0;清除速率常数K2(d-1)分别为0.030~0.101、0.022-0.074;半衰期T1/2(d)分别为6.9-23.1、9.4-31.5。
     (2)浓度对生物富集动力学参数影响表现为:暴露浓度越高,2'-OH-BDE68的BCF、K1及T1/2越小、K2越大;4'-OH-BDE90的BCF和K1越小、K2与T1/2变化不明显。OH-PBDEs(nBr=4和5)同类物的lgBCF与其lgKow之间可能不存在显著的正相关关系。
     (3)鲤鱼不同组织对2'-OH-BDE68和4'-OH-BDE90的蓄积能力大小分别表现为肝脏>肾脏>脑>肌肉、肝脏>脑>肾脏>肌肉,可能因为肝脏和肾脏是2'-OH-BDE68和4'-OH-BDE90的生物代谢靶器官,肌肉组织总量多且分布广,血脑屏障对外源性干扰物质的阻碍作用,4'-OH-BDE90具有较强的神经毒性,鲤鱼不同组织中脂肪含量对4'-OH-BDE90的蓄积量有一定的影响等。
Recently, hydroxylated polybrominated diphenyl ethers (OH-PBDEs), as emerging organic pollutants, have been detected in various environmental media and even human body. They attracted considerable concern due to their strong biological toxic effects. In order to greatly evaluate ecological risk and ultimate fate of OH-PBDEs, in the present study, bioacumulation behavior in aquatic organism(common carp) was investigated. Function mechanisms of bioaccumulation effect in liver, kidney, brain and muscle of common carp were also unveiled.
     Firstly, analytical methods of OH-PBDEs to biotic and natural water samples were established and optimized, based on previous reported methods in environmental samples. The result showed that method detection limits were0.35-10.13ng/g (lipid weight) and4.2~10.13ng/mL, respectively. OH-PBDEs congeners spiked recoveries were62.6-118.2%with good reproductivity.
     Secondly, acute toxicities (96h-LC50) of OH-PBDEs (2'-OH-BDE7,4'-OH-BDE17,2'-OH-BDE28,2'-OH-BDE68,4'-OH-BDE90and2'-OH-BDE123) to common carp were determined. Except that4'-OH-BDE17was highly toxic with LC50=1130ng/mL, the other five OH-PBDEs (2'-OH-BDE7,2'-OH-BDE28,2'-OH-BDE68,4'-OH-BDE90and2'-OH-BDE123) were virulent and the LC50values were697、854、550、644and522ng/mL, respectively. By using octanol-water partition coefficient and quantum chemical parameters as descriptors, the quantitative structure activity relationships between them and96h-lgLC50values were studied. The results showed that linear relationships were good with correlation coefficient square greater than0.96and the predicted96h-LC50values of OH-PBDEs by the obtained equations were consistent with the experimental values.
     Lastly, absorption and elimination of OH-PBDEs (2'-OH-BDE68and4'-OH-BDE90) in liver, kidney, brain and muscle of common carp were studied, using two-compartment kinetic model. A semi-static system was maintained throughout30-day exposure and60-day depuration periods. And kinetic parameters of bioaccumulation including uptake rate constant (K1), elimination rate constant (K2), bioconcentration factor (BCF) and half-life (T1/2) were obtained by linear fitting. The results showed:
     (1) The biaccumulation effects of2'-OH-BDE68and4'-OH-BDE90in each tissue of common carp followed first order reaction kinetics. Four parameters (BCF, K1, K2and T1/2) of 2'-OH-BDE68were as high as1.4×102~8.0×103(L/Kg),357.1(d-1),0.030~0.101(d-1),6.9~23.1(d), respectively.35~2.2×103(L/Kg),0.39~49.0(d-1),0.022~0.074(d-1) and9.4~31.5(d) were BCF, K1, K2and T1/2values of4'-OH-BDE90, respectively.
     (2) Exposure concentration had a significant impact on four kinetic parameters (BCF, K1, K2and T1/2). When it increased, BCF, K1and T1/2of2'-OH-BDE68and4'-OH-BDE90decreased, K2for2'-OH-BDE68enhanced and had no remarkable law for4'-OH-BDE90instead. The positive correlation relationship between lgBCF of OH-PBDEs congeners (nBr=4and5) in different tissues of common carp and their lgKow may be not notable.
     (3) The orders of distribution for2'-OH-BDE68and4'-OH-BDE90in different tissues were basically liver>kidney>brain>muscle, liver>brain>kidney>muscle, respectively. This was probably caused owing to liver and kidney being biological metabolic target organs, muscle with a large amounts and widely distributed in fish, blood brain barrier in common carp having a function to reject exogenous compounds passing into central nervous system. Perhaps there was great neurotoxicity of4'-OH-BDE90to common carp. And diversity of lipid content in tissues may be another reason.
引文
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