氧化流反应器中等量羟基暴露的老化条件对甲苯衍生二次有机气溶胶成分的影响†。

IF 2.8 Q3 ENVIRONMENTAL SCIENCES Environmental science: atmospheres Pub Date : 2024-06-07 DOI:10.1039/D4EA00027G
Hendryk Czech, Pasi Yli-Pirilä, Petri Tiitta, Mika Ihalainen, Anni Hartikainen, Eric Schneider, Patrick Martens, Andreas Paul, Thorsten Hohaus, Christopher P. Rüger, Jorma Jokiniemi, Ralf Zimmermann and Olli Sippula
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引用次数: 0

摘要

在实验室和实地研究中,氧化流动反应器(OFR)被越来越多地用于研究二次气溶胶的形成潜力和组成,其方法是在短时间内将气溶胶暴露于高浓度的氧化剂中。为了评估引发的化学反应与大气的相关性,已经开发了动力学模型来揭示大气氧化剂的生成和挥发性有机化合物(VOC)的归宿。然而,由于模型是基于气相化学的,因此还不清楚产生相同 OH 暴露的不同 OFR 条件如何影响二次气溶胶粒子相的化学和物理特性。甲苯作为二次有机气溶胶(SOAs)的前体已被充分研究,在高容量 OFR "PEAR "中以三种不同的外部 OH 反应活性(OHRext)进行老化,并在环境室中以 (1.09 ± 0.09) × 1011 s cm-3 的相同 OH 暴露进行老化。这些特定的 OFR 条件改变了所研究的甲苯衍生 SOA(tol-SOA)的大部分化学和物理特性。然而,在与大气相关的低 OHRext 条件下进行 OFR 老化并不会导致 SOA 的物理和化学性质与相同低 OHRext 条件下的室生成 SOA 最为相似。特别是,通过电喷雾(ESI)高分辨率 Orbitrap 质谱仪(HRMS)进行最详细的化学分析,在高 OHRext 条件下,偏离大气相关条件的 PEAR 和室产生的 tol-SOA 与低 OHRext 和中等 OHRext 条件下 PEAR 产生的 tol-SOA 的差异最大。我们的研究对与大气相关的 OFR 气溶胶老化概念提出了挑战,并促使我们进一步探索 OFR 条件对二次气溶胶组成的影响。
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The effect of aging conditions at equal OH exposure in an oxidation flow reactor on the composition of toluene-derived secondary organic aerosols†

Oxidation flow reactors (OFRs) have been increasingly used to conduct research on secondary aerosol formation potential and composition in laboratory and field studies by exposing aerosols to high levels of oxidants in short time periods. In order to assess the atmospheric relevance of the triggered chemical reactions, kinetic models have been developed to reveal the production of atmospheric oxidants and the fate of volatile organic compounds (VOCs). However, it is unknown how different OFR conditions generating the same OH exposure affect the chemical and physical properties of the secondary aerosol particle phase because the model is based on gas phase chemistry. Toluene as a well-investigated precursor of secondary organic aerosols (SOAs) was aged in the high-volume OFR “PEAR” at three different external OH reactivities (OHRext) and in an environmental chamber at the same OH exposure of (1.09 ± 0.09) × 1011 s cm−3. These specific OFR conditions altered the majority of the investigated chemical and physical properties of the toluene-derived SOA (tol-SOA). However, OFR-aging at low OHRext associated with atmospherically relevant conditions did not lead to physical and chemical SOA properties most similar to chamber-generated SOAs at the same low OHRext. Particularly, for the most detailed chemical analysis by electrospray (ESI) high-resolution Orbitrap mass spectrometry (HRMS), tol-SOA from the PEAR at high OHRext, deviating from atmospherically relevant conditions, and the chamber were most different to tol-SOA from the PEAR with low and medium OHRext. Our study challenges the concept of atmospherically relevant OFR aerosol aging and motivates further exploration of OFR conditions on secondary aerosol composition.

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Back cover Environmental Science: Atmospheres five years on Photodegradation of naphthalene-derived particle oxidation products. Back cover Estimation of neighborhood scale PM2.5 impacts in rural towns in the Purepecha region of Mexico.
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