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时间分辨分子特征分析表明,芳香族前体混合物经 OH 和 NO 自由基引发氧化后生成了二次有机气溶胶。

Time-Resolved Molecular Characterization of Secondary Organic Aerosol Formed from OH and NO Radical Initiated Oxidation of a Mixture of Aromatic Precursors.

机构信息

Laboratory of Atmospheric Chemistry, Paul Scherrer Institute (PSI), Villigen 5232, Switzerland.

出版信息

Environ Sci Technol. 2023 Aug 8;57(31):11572-11582. doi: 10.1021/acs.est.3c00225. Epub 2023 Jul 26.

DOI:10.1021/acs.est.3c00225
PMID:37496264
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10413940/
Abstract

Aromatic hydrocarbons (ArHCs) and oxygenated aromatic hydrocarbons (ArHC-OHs) are emitted from a variety of anthropogenic activities and are important precursors of secondary organic aerosol (SOA) in urban areas. Here, we analyzed and compared the composition of SOA formed from the oxidation of a mixture of aromatic VOCs by OH and NO radicals. The VOC mixture was composed of toluene (CH), -xylene + ethylbenzene (CH), 1,3,5-trimethylbenzene (CH), phenol (CHO), cresol (CHO), 2,6-dimethylphenol (CHO), and 2,4,6-trimethylphenol (CHO) in a proportion where the aromatic VOCs were chosen to approximate day-time traffic-related emissions in Delhi, and the aromatic alcohols make up 20% of the mixture. These VOCs are prominent in other cities as well, including those influenced by biomass combustion. In the NO experiments, large contributions from CHON dimers (C-C) were observed, corresponding to fast SOA formation within 15-20 min after the start of chemistry. Additionally, the dimers were a mixture of different combinations of the initial VOCs, highlighting the importance of exploring SOAs from mixed VOC systems. In contrast, the experiments with OH radicals yielded gradual SOA mass formation, with CHO monomers (C-C) being the dominant constituents. The evolution of SOA composition with time was tracked and a fast degradation of dimers was observed in the NO experiments, with concurrent formation of monomer species. The rates of dimer decomposition in NO SOA were ∼2-3 times higher compared to those previously determined for α-pinene + O SOA, highlighting the dependence of particle-phase reactions on VOC precursors and oxidants. In contrast, the SOA produced in the OH experiments did not dramatically change over the same time frame. No measurable effects of humidity were observed on the composition and evolution of SOA.

摘要

芳烃(ArHCs)和含氧芳烃(ArHC-OHs)由各种人为活动排放,是城市地区二次有机气溶胶(SOA)的重要前体。在这里,我们分析和比较了 OH 和 NO 自由基氧化芳烃 VOCs 混合物形成的 SOA 的组成。VOC 混合物由甲苯(CH)、二甲苯+乙苯(CH)、1,3,5-三甲苯(CH)、苯酚(CHO)、甲酚(CHO)、2,6-二甲基苯酚(CHO)和 2,4,6-三甲基苯酚(CHO)组成,芳烃 VOCs 的选择是为了近似德里白天与交通相关的排放,而芳烃醇占混合物的 20%。这些 VOCs 在其他城市也很突出,包括受生物质燃烧影响的城市。在 NO 实验中,观察到 CHON 二聚体(C-C)的大量贡献,这对应于化学起始后 15-20 分钟内快速形成 SOA。此外,二聚体是初始 VOCs 不同组合的混合物,突出了探索混合 VOC 体系 SOA 的重要性。相比之下,OH 自由基实验导致 SOA 质量逐渐形成,CHO 单体(C-C)是主要成分。跟踪 SOA 组成随时间的演变,发现 NO 实验中二聚体快速降解,同时形成单体物种。NO SOA 中二聚体分解的速率比以前确定的α-蒎烯+O SOA 高约 2-3 倍,这突出表明颗粒相反应依赖于 VOC 前体和氧化剂。相比之下,OH 实验中产生的 SOA 在相同时间内没有显著变化。没有观察到湿度对 SOA 组成和演变有可测量的影响。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9f6/10413940/6cb0f0b9a67d/es3c00225_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9f6/10413940/f84471cbe89b/es3c00225_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9f6/10413940/8013372571dd/es3c00225_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9f6/10413940/fa07008abf2f/es3c00225_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9f6/10413940/6cb0f0b9a67d/es3c00225_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9f6/10413940/f84471cbe89b/es3c00225_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9f6/10413940/8013372571dd/es3c00225_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9f6/10413940/fa07008abf2f/es3c00225_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9f6/10413940/6cb0f0b9a67d/es3c00225_0005.jpg

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