多溴联苯醚潜在替代品DOPO-HQ在环境中的稳定性研究

Environmental stability of DOPO-HQ as potential alternative to polybrominated diphenyl ethers

  • 摘要:
    目的 探讨多溴联苯醚(PBDEs)潜在替代品10-(2,5-二羟基苯基)-10-氢-9-氧杂-10-磷杂菲-10-氧化物10-(2,5-dihydroxyl phenyl)-10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,DOPO-HQ在环境中的稳定性。

    方法 根据欧盟化学品管理要求,采用经济合作与发展组织(OECD)标准方法,与pH有关的水解作用(OECD111)、测压呼吸计量法试验(OECD301F)及改进的MITI试验(Ⅱ)(OECD302C)对DOPO-HQ的水解、快速生物降解及固有生物降解性进行研究,评价DOPO-HQ的水解性和降解性,并与PBDEs进行比较。

    结果 水解结果表明,在pH7.0和pH9.0条件下DOPO-HQ快速水解,水解半衰期小于2 h;在pH4.0的酸性条件下,水解呈一级线性反应,随温度升高,水解速率加快。20℃、35℃和50℃的半衰期分别为866、201、47 h。通过累积生化需氧量评价DOPO-HQ的快速生物降解能力,结果表明,28 d的降解率仅为6.13%,不具有快速降解性。但采用多位点采集的混合接种的固有生物降解评估中,化学分析结果表明,28 d内DOPO-HQ的残留率仅为8.80%,表现出初级降解性。累积生化需氧量结果表明:在试验前20 d表现为污泥的适应期,未显示出降解性;20 d后,降解率呈明显增加趋势;28 d的降解率为12.7%,DOPO-HQ可能具有缓慢的固有生物降解能力。

    结论 DOPO-HQ在不同pH条件下水解存在一定差异,中性和碱性条件具有快速水解能力;同时表现出一定的固有生物降解可能性;较被替代品PBDEs的持久性明显减弱,可作为PBDEs的潜在替代品。

     

    Abstract:
    Objective To assess environmental stability of 10-(2, 5-dihydroxyl phenyl)-10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ) as a potential alternative to polybrominated diphenyl ethers (PBDEs).

    Methods According the requirement of Registration, Evaluation, Authorization, and Restriction of Chemicals (REACH) by the European Union, the hydrolysis and biodegradation of DOPO-HQ were evaluated by Organization for Economic Cooperation and Development (OECD) guidelines such as Hydrolysis as a Function of pH (OECD111), Manometric Respirometry Test (OECD301F), and Inherent Biodegradability:Modifed MITI Test (OECD302C); and the results were compared with those of PBDEs.

    Results In pH7.0 and pH9.0 buffers, DOPO-HQ was rapidly hydrolyzed with a halftime of hydrolysis less than 2 h. In pH4.0 buffer, the hydrolysis was a first-order reaction, and the hydrolysis rate increased with higher temperature. The halftime of hydrolysis were 866, 201, and 47 h at 20℃, 35℃, and 50℃, respectively. The results of ready biodegradability test evaluated by biochemical oxygen demand (BOD) showed that DOPO-HQ had no ready biodegradability after 28 d with a biodegradability rate of 6.13%. However, according to the inherent biodegradability test results with mixture inoculums from many sites, DOPO-HQ showed primary degradability with a chemical residue rate of 8.8% after 28d. The BOD results showed no biodegradability of DOPO-HQ for the first 20d, and the biodegradability rate obviously increased after 20d and reached 12.7% after 28d, implying slow inherent biodegradability.

    Conclusion DOPO-HQ shows varied hydrolysis properties under different pH conditions and rapid hydrolysis under neutral and basic conditions. At the same time, it shows inherent biodegradability. Compared with PBDEs, the weaker persistence of DOPOHQ is identified, thus it could be a potential alternative to PBDEs.

     

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