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水性苯二醇与有机三线态激发态和羟基自由基反应形成二次有机气溶胶。

Aqueous benzene-diols react with an organic triplet excited state and hydroxyl radical to form secondary organic aerosol.

作者信息

Smith Jeremy D, Kinney Haley, Anastasio Cort

机构信息

Department of Land, Air and Water Resources, University of California, Davis, 1 Shields Ave., Davis, CA 95616, USA.

出版信息

Phys Chem Chem Phys. 2015 Apr 21;17(15):10227-37. doi: 10.1039/c4cp06095d.

DOI:10.1039/c4cp06095d
PMID:25797024
Abstract

Chemical processing in atmospheric aqueous phases, such as cloud and fog drops, can play a significant role in the production and evolution of secondary organic aerosol (SOA). In this work we examine aqueous SOA production via the oxidation of benzene-diols (dihydroxy-benzenes) by the triplet excited state of 3,4-dimethoxybenzaldehyde, (3)DMB*, and by hydroxyl radical, ˙OH. Reactions of the three benzene-diols (catechol (CAT), resorcinol (RES) and hydroquinone (HQ)) with (3)DMB* or ˙OH proceed rapidly, with rate constants near diffusion-controlled values. The two oxidants exhibit different behaviors with pH, with rate constants for (3)DMB* increasing as pH decreases from pH 5 to 2, while rate constants with ˙OH decrease in more acidic solutions. Mass yields of SOA were near 100% for all three benzene-diols with both oxidants. We also examined the reactivity of atmospherically relevant mixtures of phenols and benzene-diols in the presence of (3)DMB*. We find that the kinetics of phenol and benzene-diol loss, and the production of SOA mass, in mixtures are generally consistent with rate constants determined in experiments containing a single phenol or benzene-diol. Combining our aqueous kinetic and SOA mass yield data with previously published gas-phase data, we estimate a total SOA production rate from benzene-diol oxidation in a foggy area with significant wood combustion to be nearly 0.6 μg mair(-3) h(-1), with approximately half from the aqueous oxidation of resorcinol and hydroquinone, and half from the gas-phase oxidation of catechol.

摘要

大气水相中的化学过程,如云滴和雾滴中的化学过程,在二次有机气溶胶(SOA)的产生和演化中可能起着重要作用。在这项工作中,我们研究了通过3,4 - 二甲氧基苯甲醛的三重激发态(3)DMB和羟基自由基˙OH氧化苯二醇(二羟基苯)来生成水相SOA。三种苯二醇(儿茶酚(CAT)、间苯二酚(RES)和对苯二酚(HQ))与(3)DMB或˙OH的反应迅速进行,速率常数接近扩散控制值。两种氧化剂在不同pH值下表现出不同的行为,(3)DMB的速率常数随着pH值从5降至2而增加,而在酸性更强的溶液中,与˙OH反应的速率常数则降低。对于两种氧化剂,所有三种苯二醇的SOA质量产率均接近100%。我们还研究了在(3)DMB存在下,与大气相关的酚类和苯二醇混合物的反应活性。我们发现,混合物中酚类和苯二醇的损失动力学以及SOA质量的产生,通常与在含有单一酚类或苯二醇的实验中测定的速率常数一致。将我们的水相动力学和SOA质量产率数据与先前发表的气相数据相结合,我们估计在一个存在大量木材燃烧的雾区,苯二醇氧化产生SOA的总速率接近0.6 μg mair(-3) h(-1),其中约一半来自间苯二酚和对苯二酚的水相氧化,另一半来自儿茶酚的气相氧化

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