کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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4438737 | 1620415 | 2012 | 11 صفحه PDF | دانلود رایگان |
Formation of secondary organic aerosol (SOA) is simulated for 14 outdoor smog chamber experiments using condensed gas-phase regulatory mechanisms and a new SOA framework. This framework is based on empirical parameterizations of independent chamber experiments and includes role of glyoxal and methylglyoxal in formation of particle aqueous-phase. To evaluate for regulatory applications, the chamber experiments include an urban non-SOA VOC mixture and NOx, with either injections of o/p-xylenes or toluene. The experiments are performed under varying conditions of relative humidity (RH) and in the presence of low initial background seed. Gas-particle partitioning of semi-volatile products into particle organic-phase is modeled using a dynamic partitioning approach with reactive uptake coefficient as the principal transport and kinetic parameter. Aqueous-phase SOA is predicted using formulations that describe the irreversible loss of both glyoxal and methylglyoxal to particle aqueous-phase. The predicted SOA mass in the new framework is evaluated using two regulatory gas-phase mechanisms – CB05 or SAPRC07 and, two regulatory parameterization schemes to predict semi-volatile product formation – an Odum-type two-product model and volatility basis-set (VBS). Predictions from the new SOA framework reproduce SOA mass within the uncertainty range of observations, irrespective of the choice of gas-phase mechanism and SOA parameterization scheme (root mean square error [RMSE] range of 0.18–3.08 μg m−3). Further, model results suggest strong possibility of dominance of bulk-process under low seed conditions and surface-uptake process under high seed for aqueous-phase SOA formation. Sensitivity analysis to the hygroscopic nature of aqueous-phase SOA indicates an uncertainty of a factor of 2 in bulk-process and surface-uptake rates. In summary, the results strongly point to considering mass-transfer and kinetic limitations in regulatory air quality models at low ambient seed concentrations and highlight the importance of aqueous-phase SOA for aromatics under high-RH conditions.
► SOA framework with dynamic partitioning and aerosol aqueous-phase processes.
► Mass-transfer limitation to partitioning in presence of non-SOA-forming HC mixture.
► Substantial aqueous-phase SOA contribution at high RH from aromatic oxidation.
► Aqueous-phase SOA: bulk-process at low seed and surface-uptake at high seed.
Journal: Atmospheric Environment - Volume 56, September 2012, Pages 250–260