4种二烷基次膦酸盐阻燃剂对斑马鱼胚胎的毒性研究

Toxicity Effects of Four Kinds of Dialkyl Phosphinate Flame Retardants on Zebrafish( Danio rerio) Embryo

二烷基次膦酸盐(DPs)作为一种新型有机磷阻燃剂正在被大量合成并应用,但关于其毒理学效应的研究还十分匮乏。研究者首次以斑马鱼胚胎作为实验模型,初步探讨了2种新型DPs阻燃剂甲基环己基次膦酸铝(AMHP)、甲基环己基次膦酸钙(CMHP)和2种已市场化生产的DPs阻燃剂甲基乙基次膦酸铝(AMEP)、二乙基次膦酸铝(ADEP)对鱼类的急性毒性效应。结果表明,AMHP和CMHP对斑马鱼胚胎无明显毒性效应;500 mg·L^(-1)的AMEP和ADEP能显著增加斑马鱼胚胎死亡率,降低其出膜率。AMHP和CMHP的水解产物甲基环己基次膦酸在浓度为1 000 mg·L^(-1)时,可使斑马鱼胚胎出膜率下降,并导致胚胎死亡,推测DPs的水解产物二烷基次膦酸是造成斑马鱼胚胎死亡的主要因素。进一步比较去除卵膜后,DPs对斑马鱼胚胎的毒性效应,发现DPs主要通过影响斑马鱼胚胎的出膜进而造成胚胎的死亡。上述研究结果从水生生物毒性的角度为DPs阻燃剂是否能作为溴化阻燃剂和传统有机磷阻燃剂的替代品提供了实验依据。

The emerging organophosphorus flame retardants, dialkyl phosphinates（DPs）, have been synthesized andused in large quantities. However, the toxicological study about them is rare. In this study, zebrafish is used as a model organism to investigate the toxicity effect of new DPs such as aluminum methylcyclohexy phosphinate（AMHP）, calcium methylcyclohexyl phosphinate（CMHP）, aluminum methylethyl phosphinate（AMEP） and aluminum diethyl phosphinate（ADEP） on aquatic organisms. The results showed that AMHP and CMHP had no significant toxic effects on zebrafish embryo, while high concentrations of AMEP and ADEP have a certain impact on zebrafish embryo. AMEP and ADEP of 500 mg·L^（-1）can significantly increase the mortality of zebrafish embryo, and decrease the rate of the hatching rate. We also studied methylcyclohexy phosphinate acid（MHPA）, the hydrolysate of AMHP and CMHP, and found that MHPA of 1 000 mg·L^（-1）exposure increased zebrafish embryo mortality while decreased its hatching rate. Furthermore, we compared the effect of DPs on normal zebrafish embryo and chorion-free zebrafish embryo. The results showed that the mortality is largely decreased after removing chorion. Thus, we speculate that the toxic effects of DPs on zebrafish embryo might be caused by DP＇s hydrolysate, and the chorion might be the direct target. These results provide evidence that dialkyl phosphinates could be a used as preeminent substitute for brominated flame retardants and traditional organophosphorus flame retardants.