Simulation of organic aerosol formation during the CalNex study: updated mobile emissions and secondary organic aerosol parameterization for intermediate-volatility organic compounds

We describe simulations using an updated version of the Community Multiscale Air Quality model version 5.3 (CMAQ v5.3) to investigate the contribution of intermediate-volatility organic compounds (IVOCs) to secondary organic aerosol (SOA) formation in southern California during the CalNex study. We first derive a model-ready parameterization for SOA formation from IVOC emissions from mobile sources. To account for SOA formation from both diesel and gasoline sources, the parameterization has six lumped precursor species that resolve both volatility and molecular structure (aromatic versus aliphatic). We also implement new mobile-source emission profiles that quantify all IVOCs based on direct measurements. The profiles have been released in SPECIATE 5.0. By incorporating both comprehensive mobile-source emission profiles for semivolatile organic compounds (SVOCs) and IVOCs and experimentally constrained SOA yields, this CMAQ configuration best represents the contribution of mobile sources to urban and regional ambient organic aerosol (OA). In the Los Angeles region, gasoline sources emit 4 times more non-methane organic gases (NMOGs) than diesel sources, but diesel emits roughly 3 times more IVOCs on an absolute basis. The revised model predicts all mobile sources (including on- and off-road gasoline, aircraft, and on- and off-road diesel) contribute ∼1 µg m−3 to the daily peak SOA concentration in Pasadena. This represents a ∼70 % increase in predicted daily peak SOA formation compared to the base version of CMAQ. Therefore, IVOCs in mobile-source emissions contribute almost as much SOA as traditional precursors such as single-ring aromatics. However, accounting for these emissions in CMAQ does not reproduce measurements of either ambient SOA or IVOCs. To investigate the potential contribution of other IVOC sources, we performed two exploratory simulations with varying amounts of IVOC emissions from nonmobile sources. To close the mass balance of primary hydrocarbon IVOCs, IVOCs would need to account for 12 % of NMOG emissions from nonmobile sources (or equivalently 30.7 t d−1 in the Los Angeles–Pasadena region), a value that is well within the reported range of IVOC content from volatile chemical products. To close the SOA mass balance and also explain the mildly oxygenated IVOCs in Pasadena, an additional 14.8 % of nonmobile-source NMOG emissions would need to be IVOCs (assuming SOA yields from the mobile IVOCs apply to nonmobile IVOCs). However, an IVOC-to-NMOG ratio of 26.8 % (or equivalently 68.5 t d−1 in the Los Angeles–Pasadena region) for nonmobile sources is likely unrealistically high. Our results highlight the important contribution of IVOCs to SOA production in the Los Angeles region but underscore that other uncertainties must be addressed (multigenerational aging, aqueous chemistry and vapor wall losses) to close the SOA mass balance. This research also highlights the effectiveness of regulations to reduce mobile-source emissions, which have in turn increased the relative importance of other sources, such as volatile chemical products.

Simulation of organic aerosol formation during the CalNex study: updated mobile emissions and simplified secondary organic aerosol parameterization for intermediate volatility organic compounds

We describe simulations using an updated version of the Community Multiscale Air Quality model version 5.3 (CMAQ v5.3) to investigate the contribution of intermediate volatile organic compounds (IVOCs) to secondary organic aerosol formation (SOA) in Southern California during the CalNex study. We first derive a model-ready parameterization for SOA formation from IVOC emissions from mobile sources. To account for SOA formation from both diesel and gasoline sources, the parameterization has six lumped precursor species that account for differences in both volatility and molecular structure (aromatic versus aliphatic) of unspeciated IVOC emissions. We also implement new mobile source emission profiles that quantify all IVOCs based on direct measurements. The profiles have been released in SPECIATE 5.0. In the Los Angeles region, gasoline sources emit 4 times more non-methane organic gases (NMOG) than diesel sources, but diesel emits roughly 3 times more IVOCs on an absolute basis. When accounting for IVOCs, the model predicts all mobile sources (including on- and off-road gasoline, aircraft and on- and off-road diesel) contribute ~1 μg m−3 of SOA in Pasadena, CA, which corresponds to 12 % of the measured SOA concentrations during CalNex. Adding mobile-source IVOCs increases the predicted SOA concentration by ~ 70 %. Therefore, IVOCs in mobile source emissions contribute almost as much SOA as traditional precursors such as single-ring aromatics. However, addition of these emissions still does not close either the ambient SOA or IVOC mass balance. To explore the potential contribution of other IVOC sources, we perform two exploratory simulations with varying amounts of IVOC emissions from non-mobile sources. To close the mass balance of primary hydrocarbon IVOCs, IVOCs would need to account for 12 % of NMOG emissions from non-mobile sources (or equivalently 30.7 Ton day−1 in Los Angeles-Pasadena region), a value that is well within the reported range of IVOC content from volatile chemical products. To close the SOA mass balance and explain mildly oxygenated IVOCs in Pasadena, an additional 14.8 % of non-mobile source NMOG emissions would need to be IVOCs, but assigning an IVOC-to-NMOG ratio of 26.8 % (or equivalently 68.5 Ton day−1 in Los Angeles-Pasadena region) for non-mobile sources seems unrealistically high. By incorporating the most comprehensive mobile emissions profiles for SVOCs and IVOCs along with experimentally constrained SOA yields from mobile IVOCs, this CMAQ configuration represents the most accurate photochemical model prediction of the contribution of mobile sources to urban and regional ambient OA to date. Our results highlight the important contribution of IVOCs to SOA production in Los Angeles region, but also underscore that other uncertainties must be addressed (multigenerational aging, aqueous chemistry, and vapor wall losses) to close the SOA mass balance. This research also highlights the effectiveness of regulations to reduce mobile source emissions, which have, in turn, increased the relative importance of other sources, such as volatile chemical products.