Nitrogen-containing secondary organic aerosol formation by acrolein reaction with ammonia/ammonium

Li, Zhijian; Nizkorodov, Sergey A.; Chen, Hong; Lu, Xiaohui; Yang, Xin; Chen, Jianmin

Ammonia-driven carbonyl-to-imine conversion is an important formation pathway to the nitrogen-containing organic compounds (NOCs) in secondary organic aerosols (SOAs). Previous studies have mainly focused on the dicarbonyl compounds as the precursors of light-absorbing NOCs. In this work, we investigated whether acrolein could also act as an NOC precursor. Acrolein is the simplest inline-formulaα, inline-formulaβ-unsaturated mono-carbonyl compound, and it is ubiquitous in the atmosphere. Experiments probing multiphase reactions of acrolein as well as bulk aqueous-phase experiments were carried out to study the reactivity of acrolein towards ammonia and ammonium ions. Molecular characterization of the products based on gas chromatography mass spectrometry, high-resolution mass spectrometry, surface-enhanced Raman spectrometry and ultraviolet/visible spectrophotometry was used to propose possible reaction mechanisms.

We observed 3-methylpyridine (commonly known as 3-picoline) in the gas phase in Tedlar bags filled with gaseous acrolein and ammonia or ammonium aerosols. In the ammonium-containing aqueous phase, oligomeric compounds with formulas (inline-formulaC3H4O)inline-formulam(inline-formulaC3H5N)inline-formulan and pyridinium compounds like (inline-formulaC3H4O)inline-formula2inline-formulaC6H8N+ were observed as the products. The pathway to 3-methylpyridine was proposed to be the intramolecular carbon–carbon addition of the hemiaminal, which resulted from sequential carbonyl-to-imine conversions of acrolein molecules. The 3-methylpyridine was formed in the aqueous phase, but some of the 3-methylpyridine could revolatilize to the gas phase, explaining the observation of gaseous 3-methylpyridine in the bags. The (inline-formulaC3H4O)inline-formula2inline-formulaC6H8N+ was a carbonyl-to-hemiaminal product from acrolein dimer and 3-methylpyridine, while the oligomeric products of (inline-formulaC3H4O)inline-formulam(inline-formulaC3H5N)inline-formulan were polymers of acroleins and propylene imines formed via carbonyl-to-imine conversion and condensation reactions. The pH value effect on the liquid products was also studied in the bulk aqueous-phase experiments. While the oligomeric compounds were forming in both acidic and alkaline conditions, the pyridinium products favored moderately acidic conditions. Both the oligomeric products and the pyridinium salts are light-absorbing materials. This work suggests that acrolein may serve as a precursor of light-absorbing heterocyclic NOCs in SOA. Therefore, secondary reactions of inline-formulaα, inline-formulaβ-unsaturated aldehydes with reduced nitrogen should be taken into account as a source of light-absorbing NOCs in SOA.



Li, Zhijian / Nizkorodov, Sergey A. / Chen, Hong / et al: Nitrogen-containing secondary organic aerosol formation by acrolein reaction with ammonia/ammonium. 2019. Copernicus Publications.


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