Abstract

<strong class="journal-contentHeaderColor">Abstract.</strong> Organic aerosol (OA) is a significant part of urban fine particulate matter (PM<sub>2.5</sub>) and a lack of detailed knowledge of their sources has increasingly hindered the improvement of air quality in China in recent years as significant reductions have been achieved in inorganic ion constituents. In this study, a wide range of organic molecular markers in PM<sub>2.5</sub> were monitored with a bihourly time resolution using a Thermal desorption Aerosol Gas chromatograph system (TAG) in urban Shanghai in winter 2019. The molecular marker data have provided a unique source tracking ability in characterizing the evolution of organic aerosols during nine wintertime episodic events. Episodes primarily influenced by local air masses were characterized with higher proportions and mass increments of secondary OA. Rapid elevation in both absolute mass concentration and relative proportion was observed for primary and secondary OA markers indicative of vehicle emissions (e.g., alkanes, hopanes, and 2,3-dihydroxy-4-oxopentanoic acid), as well as cooking activities (e.g., saturated and unsaturated fatty acids, and C9 acids). In comparison, episodes under significant influences of transported air mass were typically associated with a predominant PM<sub>2.5</sub> contribution from secondary inorganic aerosols and enhanced OA contribution from biomass burning activities. The latter was evident from the tracer data (e.g., levoglucosan, aromatic polycarboxylic acids, and nitro-aromatic compounds). Secondary OA markers associated with later generation products of hydrocarbon oxidation process, such as C<sub>3&ndash;5</sub> dicarboxylic acids, were the most deficient during local episodes while notably enhanced during the episodes under influence of transported air masses, reflecting different extent and pathways of atmospheric aging processing. The ability of distinguishing the variations of OA evolution during different types of episodes demonstrates the value of online organic molecular measurements to episodic analysis. The results indicate that control of local urban sources such as vehicular and cooking emissions would lessen severity of local episodes while regional control of precursors for secondary inorganic aerosols and biomass burning activities would reduce PM<sub>2.5</sub> episodes under synoptic conditions conducive for regional transport.

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