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首页> 外文期刊>Environmental Science & Technology >Effects of Atmospheric Water on OH-initiated Oxidation of Organophosphate Flame Retardants: A DFT Investigation on TCPP
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Effects of Atmospheric Water on OH-initiated Oxidation of Organophosphate Flame Retardants: A DFT Investigation on TCPP

机译:大气水对有机磷酸酯阻燃剂的OH引发氧化的影响:TCPP的DFT研究

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摘要

Tris(2-chIoroisopropyl) phosphate (TCPP), a widely used organophosphate flame retardant, has been recognized as an important atmospheric pollutant. It is notable that TCPP has potential for long-range atmospheric transport. However, its atmospheric fate is unknown, restricting its environmental risk assessment. Herein we performed quantum chemical calculations to investigate the atmospheric transformation mechanisms and kinetics of TCPP initiated by · OH in the presence of O_2/N0/NO_2, and the effects of ubiquitous water on these reactions. Results show the Η-abstraction pathways are the most favorable for the titled reaction. The calculated gaseous rate constant and lifetime at 298 Κ are 1.7 X 10~(-10) cm3molecule~(-1) s~(-1) and 1.7 h, respectively. However, when considering atmospheric water, the corresponding lifetime is about 0.5-20.2 days. This study reveals for the first time that water has a negative role in the OH-initiated degradation of TCPP by modifying the stabilities of prereactive complexes and transition states via forming hydrogen bonds, which unveils one underlying mechanism for the observed persistence of TCPP in the atmosphere. Water also influences secondary reaction pathways of selected TCPP radicals formed from the primary Η-abstraction. These results demonstrate the importance of water in the evaluation of the atmospheric fate of newly synthesized chemicals and emerging pollutants.
机译:磷酸三(2-氯异丙基)酯(TCPP),一种广泛使用的有机磷酸酯阻燃剂,被认为是重要的大气污染物。值得注意的是,TCPP具有远距离大气传输的潜力。但是,其大气命运尚不明了,这限制了其环境风险评估。在这里,我们进行了量子化学计算,以研究在O_2 / N0 / NO_2存在下·OH引发的TCPP的大气转化机理和动力学,以及普遍存在的水对这些反应的影响。结果表明,H-提取途径对于标题反应是最有利的。在298Κ时计算出的气体速率常数和寿命分别为1.7 X 10〜(-10)cm3分子〜(-1)s〜(-1)和1.7 h。但是,考虑大气水时,相应的寿命约为0.5-20.2天。这项研究首次揭示了水在氢引发的TCPP降解中具有消极作用,它通过形成氢键来改变预反应复合物的稳定性和过渡态,从而揭示了TCPP在大气中的持久性的一种潜在机制。 。水还影响由主要的H-抽象形成的所选TCPP自由基的次要反应途径。这些结果证明了水在评估新合成化学品和新兴污染物的大气命运方面的重要性。

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  • 来源
    《Environmental Science & Technology》 |2017年第9期|5043-5051|共9页
  • 作者单位

    Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024, China ,State Environmental Protection Key Laboratory of Wetland Ecology and Vegetation Restoration, School of Environment, Northeast Normal University, Changchun 130117, China;

    Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024, China;

    Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024, China;

    State Environmental Protection Key Laboratory of Wetland Ecology and Vegetation Restoration, School of Environment, Northeast Normal University, Changchun 130117, China;

    Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024, China;

    Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024, China;

    Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024, China;

    Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024, China;

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