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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Modeling the OH-Initiated Oxidation of Mercury in the Global Atmosphere without Violating Physical Laws
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Modeling the OH-Initiated Oxidation of Mercury in the Global Atmosphere without Violating Physical Laws

机译：在没有违反物理法律的情况下建模OH-发起的汞氧化汞

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In 2005, Calvert and Lindberg (Calvert, J. G.; Lindberg, S. E. Atmos. Environ. 2005, 39, 3355-3367) wrote that the use of laboratory-derived rate constants for OH + Hg(0) "...to determine the extent of Hg removal by OH in the troposphere will greatly overestimate the importance of Hg removal by this reaction." The HOHg center dot intermediate formed from OH + Hg will mostly fall apart in the atmosphere before it can react. By contrast, in laboratory experiments, Calvert and Lindberg expected HOHg center dot to react with radicals (whose concentrations are much higher than in the atmosphere). Yet, almost all models of oxidation of Hg(0) ignore the argument of Calvert and Lindberg. We present a way for modelers to include the OH + Hg reaction while accounting quantitatively for the dissociation of HOHg center dot. We use high levels of quantum chemistry to establish the HO-Hg bond energy as 11.0 kcal/mol and calculate the equilibrium constant for OH + Hg = HOHg center dot. Using the measured rate constant for the association of OH with Hg, we determine the rate constant for HOHg center dot dissociation. Theory is also used to demonstrate that HOHg center dot forms stable compounds, HOHgY, with atmospheric radicals (Y = NO2, HOO center dot, CH3OO center dot, and BrO). We then present rate constants for use in modeling OH-initiated oxidation of Hg(0). We use this mechanism to model the global oxidation of Hg(0) in the period 2013-2015 using the GEOS-Chem 3D model of atmospheric chemistry. Because of the rapid dissociation of HOHg center dot, OH accounts for <1% of the global oxidation of Hg(0) to Hg(II), while Br atoms account for 97%.
机译：2005年，Calvert和Lindberg（Calvert，JG; Lindberg，SE Atmos。环境。2005,39,3355-3367）写道，使用OH + Hg（0）“的实验室衍生的速率常数......以确定在对流层中，oh of of o的hg脱落将极大地高估通过这种反应的Hg清除的重要性。“由OH + Hg形成的HoHG中心点中间体将在大气中脱落，然后在其反应之前将在大气中分开。相比之下，在实验室实验中，Calvert和Lindberg预期的Hohg中心点与自由基反应（其浓度远高于大气中）。然而，几乎所有氧化的HG（0）模型都忽略了Calvert和Lindberg的论点。我们为建模者提供了一种方法，包括OH + HG反应，同时定量占HOHG中心点的解离。我们使用高水平的量子化学来建立HO-HG键能为11.0kcal / mol，并计算OH + HG = HOHG中心点的平衡常数。使用测量的速率常数OH与Hg，我们确定HOHG中心点解离的速率常数。理论也用于证明HOHG中心点形成稳定的化合物，HOHGY，具有大气自由基（Y = NO2，HOO中心点，CH3OO中心点和兄弟）。然后，我们存在用于模拟Hg（0）的氧化氧化的速率常数。我们使用这种机制来利用大气化学的Geos-Chem 3D模型在2013 - 2015年期间模拟HG（0）的全局氧化。由于HOHG中心点的快速解散，OH占HG（0）至HG（II）的全球氧化的1％，而BR原子占97％。

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