Smith Jeremy D, Kinney Haley, Anastasio Cort
Department of Land, Air and Water Resources, University of California, Davis, 1 Shields Ave., Davis, CA 95616, USA.
Phys Chem Chem Phys. 2015 Apr 21;17(15):10227-37. doi: 10.1039/c4cp06095d.
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.
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