Modeling Atmospheric Secondary Organic Aerosol Dynamics Through Chemistry, Emissions, and Partition Theory PDF Download

Author: Wayne Li-wen Chang
Publisher:
ISBN: 9781124791869
Category :
Languages : en
Pages : 89

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Book Description
The detrimental impact on both human health and global climate of atmospheric particular matter (PM) is now well-established. Among the various classifications of PM, a significant portion is comprised of secondary organic aerosol (SOA). Despite its importance, there are still much uncertainty regarding the formation and evolution of SOA in the atmosphere, beginning with the oxidation of organic gases that leads to semi-volatile and low volatility products. The need to further improve the current knowledge SOA is made apparent by the observed large discrepancy between model predictions and field measurements of SOA. Proposed explanations behind the orders of magnitude underprediction of ambient SOA levels by state-of-the-art airshed models include: missing particle-forming oxidized organic products, unidentified SOA precursor emissions, and issues related to the fundamentals of current SOA partition theory, all of which are considered in this study to develop corresponding improvements to the latest airshed models. The model used in this study is the UCI-CIT airshed model, and the improvement scenario tests are set in the urban region of South Coast Air Basin of California. Recent chamber results have shown that the original implementation of alkane-derived SOA provided an underestimate for what was likely to be occurring in urban atmospheres. Thus, the original chemical mechanism is revised to include higher generation products of medium- and long-chain alkanes that can contribute to SOA in this study. Primary organic aerosol (POA) has been identified to be able to evaporate with dilution; therefore, test cases are developed that treat fractions of POA as semi-volatile, a source of SOA, rather than nonvolatile. While current atmospheric models assume that SOA are liquids into which semi-VOCs undergo equilibrium partitioning and grow the particles, recent laboratory and field experiments have shown otherwise. Hence, a new kinetics-driven partition theory is developed and analyzed against the original formulations. The results from the expanded chemical mechanism to include higher-generation products of alkane in the atmosphere shows that only the tetrahydrofurans will contribute to SOA and those contributions are only a small fraction compared to other SOA sources in the model, contrary to the prediction made based on chamber experiments and box models. In the tests for redistribution of POA as gas-phase parent VOCs sources, POA decreased with no commensurate increase in SOA. This is essentially due to the fact that the amount of mass that the POA can contribute is a small fraction of that already in the gas-phase parent VOC pool. Finally, using the newly developed kinetically determined SOA growth mechanism, to achieve the same level of predicted SOA levels as the original equilibrium approach requires 40-50% of SOA parent species to be allocated to the particle phase. The new formulation of SOA partition behavior based on kinetics will require the measurement of new input data and the corresponding parameterization for models in the future. The implication of this new approach should demand wider attention from the community.