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WSOCs 和 pH 值对硝酸铵气溶胶的晶化作用:对二次气溶胶形成的深入了解。

Role of WSOCs and pH on Ammonium Nitrate Aerosol Efflorescence: Insights into Secondary Aerosol Formation.

机构信息

Institute of Chemical Physics, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China.

出版信息

Environ Sci Technol. 2023 Dec 5;57(48):20074-20084. doi: 10.1021/acs.est.3c07603. Epub 2023 Nov 16.

Abstract

Efflorescence of ammonium nitrate (AN) aerosols significantly impacts atmospheric secondary aerosol formation, climate, and human health. We investigated the effect of representative water-soluble organic compounds (WSOCs) (sucralose (SUC), glycerol (GLY), and citric acid (CA) on AN:WSOC aerosol efflorescence using vacuum Fourier transform infrared spectroscopy. Combining efflorescence relative humidity (ERH) measurements, heterogeneous nucleation rates, and model predictions, we found that aerosol viscosity, correlating with molecular diffusion, effectively predicted ERH variations among the AN:WSOC aerosols. WSOCs with higher viscosity (SUC and CA) hindered efflorescence, while GLY with a lower viscosity showed a minor effect. At a low AN:CA molar ratio (10:1), CA promoted ERH, likely due to CA crystallization. Increasing the droplet pH inhibited AN:CA aerosol efflorescence. In contrast, for AN:SUC and AN:GLY aerosols, efflorescence is pH-insensitive. With the addition of trivial sulfate, AN:SUC droplets exhibited two-stage efflorescence, coinciding with ammonium sulfate and AN efflorescence. Given the atmospheric abundance, the morphology, phase, and mixing state of nitrate aerosols are significant for atmospheric chemistry and physics. Our results suggest that AN:WSOCs aerosols can exist in the amorphous phase in the atmosphere, with efflorescence behavior depending on the aerosol composition, viscosity, pH, and the cation and anion interactions in a complex manner.

摘要

硝酸铵(AN)气溶胶的花出显著影响大气二次气溶胶形成、气候和人类健康。我们使用真空傅里叶变换红外光谱研究了具有代表性的水溶性有机化合物(WSOC)(蔗糖(SUC)、甘油(GLY)和柠檬酸(CA)对 AN:WSOC 气溶胶花出的影响。结合花出相对湿度(ERH)测量、非均相成核速率和模型预测,我们发现气溶胶粘度与分子扩散相关,可有效预测 AN:WSOC 气溶胶 ERH 的变化。粘度较高的 WSOC(SUC 和 CA)阻碍了花出,而粘度较低的 GLY 则影响较小。在低 AN:CA 摩尔比(10:1)下,CA 促进了 ERH,可能是由于 CA 结晶。增加液滴 pH 值会抑制 AN:CA 气溶胶花出。相比之下,对于 AN:SUC 和 AN:GLY 气溶胶,花出对 pH 值不敏感。加入少量硫酸盐后,AN:SUC 液滴表现出两阶段花出,与硫酸铵和 AN 的花出相吻合。鉴于大气中的丰度,硝酸盐气溶胶的形态、相态和混合状态对大气化学和物理都很重要。我们的结果表明,AN:WSOC 气溶胶在大气中可能处于无定形相,花出行为取决于气溶胶组成、粘度、pH 值以及阳离子和阴离子之间的复杂相互作用。

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