Preprints
https://doi.org/10.5194/egusphere-2022-681
https://doi.org/10.5194/egusphere-2022-681
 
18 Aug 2022
18 Aug 2022

Modeling the Influence of Chain Length on SOA Formation via Multiphase Reactions of Alkanes

Azad Madhu, Myoseon Jang, and David Deacon Azad Madhu et al.
  • Engineering School of Sustainable Infrastructure and Environment, University of Florida, Gainesville, 32608, United States of America

Abstract. Secondary Organic Aerosol (SOA) from diesel fuel is known to be significantly sourced from the atmospheric oxidation of aliphatic hydrocarbons. In this study, the formation of linear-alkane SOA was predicted using the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model that simulated multiphase reactions of hydrocarbons. In the model, the formation of oxygenated products from the photooxidation of linear alkanes was simulated using a near-explicit gas kinetic mechanism. Autoxidation paths integrated with alkyl peroxy radicals were added to the Master Chemical Mechanismv3.3.1 to improve the formation of low volatility products in the gas phase and better predict SOA mass. The resulting gas products were then classified into volatility-reactivity based lumping groups that are linked to mass-based stoichiometric coefficients. The SOA mass in the UNIPAR model is produced via three major pathways: partitioning of gaseous oxidized products onto both the organic and wet inorganic phases; oligomerization in organic phase; and reactions in the wet inorganic phase (acid-catalyzed oligomerization and organosulfate formation). The model performance was demonstrated for SOA data that were produced through the photooxidation of a homologous series of linear alkanes ranging from C9 to C15 under varying environments (NOx levels, temperature, and inorganic seed conditions) in a large outdoor photochemical smog chamber. The product distributions of linear alkanes were mathematically predicted as a function of carbon number using an incremental volatility coefficient (IVC) to cover a wide range of alkane lengths. The prediction of alkane SOA using the incremental volatility-based product distributions, which were obtained with C9–C12 alkanes, was evaluated for prediction of C13 and C15 chamber data and further extrapolated to predict the SOA from longer chain alkanes (C15) that can be found in diesel. The model simulation of linear alkanes in diesel fuel suggests that SOA mass is mainly produced by alkanes C15 and higher. Alkane SOA is insignificantly impacted by the reactions of organic species in the wet inorganic phase due to the hydrophobicity of products, but significantly influenced by gas-particle partitioning.

Azad Madhu et al.

Status: final response (author comments only)

Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor | : Report abuse
  • RC1: 'Comment on egusphere-2022-681', Anonymous Referee #1, 14 Sep 2022
  • RC2: 'Comment on egusphere-2022-681', Anonymous Referee #2, 20 Sep 2022

Azad Madhu et al.

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Short summary
SOA formation is simulated using the UNIPAR model for series of linear alkanes. The inclusion of autoxidation reactions within the explicit gas mechanisms of C9–C12 was found to significantly improve predictions. Available product distributions were extrapolated, with an incremental volatility coefficient(IVC), to predict SOA formation of alkanes without explicit mechanisms. These product distributions were used to simulate SOA formation from C13 and C15 and had good agreement with chamber data.