The prediction of Secondary Organic Aerosol (SOA) in regional scales is traditionally performed by using gas-particle partitioning models. In the presence of inorganic salted wet aerosols, aqueous reactions of semivolatile organic compounds can also significantly contribute to SOA formation. The UNIfied Partitioning-Aerosol phase Reaction (UNIPAR) model utilizes the explicit gas mechanism to better predict SOA formation from multiphase reactions of hydrocarbons. In this work, the UNIPAR model was incorporated with the Comprehensive Air Quality Model with Extensions (CAMx) to predict the ambient concentration of organic matter (OM) in urban atmospheres during the Korean-United States Air Quality (2016 KORUS-AQ) campaign. The SOA mass predicted with the CAMx-UNIPAR model changed with varying levels of humidity and emissions and in turn, has the potential to improve the accuracy of OM simulations. The CAMx-UNIPAR model significantly improved the simulation of SOA formation under the wet condition, which often occurred during the KORUS-AQ campaign, through the consideration of aqueous reactions of reactive organic species and gas-aqueous partitioning. The contribution of aromatic SOA to total OM was significant during the low-level transport/haze period (24-31 May 2016) because aromatic oxygenated products are hydrophilic and reactive in aqueous aerosols. The OM mass predicted with the CAMx-UNIPAR model was compared with that predicted with the CAMx model integrated with the conventional two product model (SOAP). Based on estimated statistical parameters to predict OM mass, the performance of CAMx-UNIPAR was noticeably better than the conventional CAMx model although both SOA models underestimated OM compared to observed values, possibly due to missing precursor hydrocarbons such as sesquiterpenes, alkanes, and intermediate VOCs. The CAMx-UNIPAR model simulation suggested that in the urban areas of South Korea, terpene and anthropogenic emissions significantly contribute to SOA formation while isoprene SOA minimally impacts SOA formation.
more »
« less
A Scheme for Representing Aromatic Secondary Organic Aerosols in Chemical Transport Models: Application to Source Attribution of Organic Aerosols Over South Korea During the KORUS‐AQ Campaign
Abstract We present a new volatility basis set (VBS) representation of aromatic secondary organic aerosol (SOA) for atmospheric chemistry models by fitting a statistical oxidation model with aerosol microphysics (SOM‐TOMAS) to results from laboratory chamber experiments. The resulting SOM‐VBS scheme also including previous work on SOA formation from semi‐ and intermediate volatile organic compounds (S/IVOCs) is implemented in the GEOS‐Chem chemical transport model and applied to simulation of observations from the Korea‐United States Air Quality Study (KORUS‐AQ) field campaign over South Korea in May–June 2016. Our SOM‐VBS scheme can simulate the KORUS‐AQ organic aerosol (OA) observations from aircraft and surface sites better than the default schemes used in GEOS‐Chem including for vertical profiles, diurnal cycle, and partitioning between hydrocarbon‐like OA and oxidized OA. Our results confirm the important contributions of oxidized primary OA and aromatic SOA found in previous analyses of the KORUS‐AQ data and further show a large contribution from S/IVOCs. Model source attribution of OA in surface air over South Korea indicates one third from domestic anthropogenic emissions, with a large contribution from toluene and xylenes, one third from external anthropogenic emissions, and one third from natural emissions.
more »
« less
- Award ID(s):
- 2206655
- PAR ID:
- 10522072
- Publisher / Repository:
- American Geophysical Union
- Date Published:
- Journal Name:
- Journal of Geophysical Research: Atmospheres
- Volume:
- 128
- Issue:
- 8
- ISSN:
- 2169-897X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract. Accurate representation of aerosol optical properties is essential for the modeling and remote sensing of atmospheric aerosols. Although aerosol optical properties are strongly dependent upon the aerosol size distribution, the use of detailed aerosol microphysics schemes in global atmospheric models is inhibited by associated computational demands. Computationally efficient parameterizations for aerosol size are needed. Inthis study, airborne measurements over the United States (DISCOVER-AQ) andSouth Korea (KORUS-AQ) are interpreted with a global chemical transport model (GEOS-Chem) to investigate the variation in aerosol size when organicmatter (OM) and sulfate–nitrate–ammonium (SNA) are the dominant aerosol components. The airborne measurements exhibit a strong correlation (r=0.83) between dry aerosol size and the sum of OM and SNA mass concentration (MSNAOM). A global microphysical simulation(GEOS-Chem-TOMAS) indicates that MSNAOM and theratio between the two components (OM/SNA) are the major indicators for SNA and OM dry aerosol size. A parameterization of the dry effective radius (Reff) for SNA and OM aerosol is designed to represent the airborne measurements (R2=0.74; slope = 1.00) and the GEOS-Chem-TOMAS simulation (R2=0.72; slope = 0.81). When applied in the GEOS-Chem high-performance model, this parameterization improves the agreement between the simulated aerosol optical depth (AOD) and the ground-measured AOD from the Aerosol Robotic Network (AERONET; R2 from 0.68 to 0.73 and slope from 0.75 to 0.96). Thus, this parameterization offers a computationally efficient method to represent aerosol size dynamically.more » « less
-
Abstract. Tropospheric ozone is a major air pollutant and greenhouse gas. It is also the primary precursor of OH, the main tropospheric oxidant. Global atmospheric chemistry models show large differences in their simulations of tropospheric ozone budgets. Here we implement the widely used GEOS-Chem atmospheric chemistry module as an alternative to CAM-chem within the Community Earth System Model version 2 (CESM2). We compare the resulting GEOS-Chem and CAM-chem simulations of tropospheric ozone and related species within CESM2 to observations from ozonesondes, surface sites, the ATom-1 aircraft campaign over the Pacific and Atlantic, and the KORUS-AQ aircraft campaign over the Seoul Metropolitan Area. We find that GEOS-Chem and CAM-chem within CESM2 have similar tropospheric ozone budgets and concentrations usually within 5 ppb but important differences in the underlying processes including (1) photolysis scheme (no aerosol effects in CAM-chem), (2) aerosol nitrate photolysis, (3) N2O5 cloud uptake, (4) tropospheric halogen chemistry, and (5) ozone deposition to the oceans. Global tropospheric OH concentrations are the same in both models, but there are large regional differences reflecting the above processes. Carbon monoxide is lower in CAM-chem (and lower than observations), at least in part because of higher OH concentrations in the Northern Hemisphere and insufficient production from isoprene oxidation in the Southern Hemisphere. CESM2 does not scavenge water-soluble gases in convective updrafts, leading to some upper-tropospheric biases. Comparison to KORUS-AQ observations shows an overestimate of ozone above 4 km altitude in both models, which at least in GEOS-Chem is due to inadequate scavenging of particulate nitrate in convective updrafts in CESM2, leading to excessive NO production from nitrate photolysis. The KORUS-AQ comparison also suggests insufficient boundary layer mixing in CESM2. This implementation and evaluation of GEOS-Chem in CESM2 contribute to the MUSICA vision of modularizing tropospheric chemistry in Earth system models.more » « less
-
Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for isoprene SOA formation coupled to a detailed gas-phase isoprene oxidation scheme. The mechanism is based on aerosol reactive uptake coefficients (γ) for water-soluble isoprene oxidation products, including sensitivity to aerosol acidity and nucleophile concentrations. We apply this mechanism to simulation of aircraft (SEAC4RS) and ground-based (SOAS) observations over the southeast US in summer 2013 using the GEOS-Chem chemical transport model. Emissions of nitrogen oxides (NOx ≡ NO + NO2) over the southeast US are such that the peroxy radicals produced from isoprene oxidation (ISOPO2) react significantly with both NO (high-NOx pathway) and HO2 (low-NOx pathway), leading to different suites of isoprene SOA precursors. We find a mean SOA mass yield of 3.3 % from isoprene oxidation, consistent with the observed relationship of total fine organic aerosol (OA) and formaldehyde (a product of isoprene oxidation). Isoprene SOA production is mainly contributed by two immediate gas-phase precursors, isoprene epoxydiols (IEPOX, 58 % of isoprene SOA) from the low-NOx pathway and glyoxal (28 %) from both low- and high-NOx pathways. This speciation is consistent with observations of IEPOX SOA from SOAS and SEAC4RS. Observations show a strong relationship between IEPOX SOA and sulfate aerosol that we explain as due to the effect of sulfate on aerosol acidity and volume. Isoprene SOA concentrations increase as NOx emissions decrease (favoring the low-NOx pathway for isoprene oxidation), but decrease more strongly as SO2 emissions decrease (due to the effect of sulfate on aerosol acidity and volume). The US Environmental Protection Agency (EPA) projects 2013–2025 decreases in anthropogenic emissions of 34 % for NOx (leading to a 7 % increase in isoprene SOA) and 48 % for SO2 (35 % decrease in isoprene SOA). Reducing SO2 emissions decreases sulfate and isoprene SOA by a similar magnitude, representing a factor of 2 co-benefit for PM2.5 from SO2 emission controls.more » « less
-
Organic aerosol (OA) is an air pollutant ubiquitous in urban atmospheres. Urban OA is usually apportioned into primary OA (POA), mostly emitted by mobile sources, and secondary OA (SOA), which forms in the atmosphere due to oxidation of gas-phase precursors from anthropogenic and biogenic sources. By performing coordinated measurements in the particle phase and the gas phase, we show that the alkylperoxy radical chemistry that is responsible for low-temperature ignition also leads to the formation of oxygenated POA (OxyPOA). OxyPOA is distinct from POA emitted during high-temperature ignition and is chemically similar to SOA. We present evidence for the prevalence of OxyPOA in emissions of a spark-ignition engine and a next-generation advanced compression-ignition engine, highlighting the importance of understanding OxyPOA for predicting urban air pollution patterns in current and future atmospheres.more » « less
An official website of the United States government

