Impacts of Phase State and Water Content on Secondary Organic Aerosol Formation and Partitioning
Principal Investigator
Manabu Shiraiwa
— Regents of the University of California, Irvine
Co-Investigators
James Smith — University of California, Irvine
Annmarie Carlton — University of California, Irvine
Sergey Nizkorodov — University of California, Irvine
Abstract
Secondary organic aerosols (SOA) account for a major fraction of particulate matter in the atmosphere, affecting climate, air quality, and public health. SOA formation and evolution are highly complex processes involving both chemical reactions and transport of molecules in air, at particle surfaces, and within particles. The state of the matter, or “phase state,” comprising SOA can vary from a liquid, over an amorphous semi-solid, to a glassy solid, depending on chemical composition, water content, relative humidity (RH), and temperature. The occurrence of glassy and amorphous semi-solid states can pose limitations on the rate of transport of molecules, affecting gas-particle interactions and challenging the treatment of SOA in atmospheric models. There is still a lack of understanding of the impacts of phase state and water content on SOA processes. The first objective of this project is to improve fundamental understanding of the interplay of the phase state of particles and water content on the evolution of SOA mass and particle size distribution. We will analyze the existing literature on RH effects on SOA formation and perform additional targeted laboratory experiments using state-of-the-art instrumentation. Data from lab experiments performed at different RH will be analyzed using a novel framework developed by the PI, called the “molecular corridor approach,” in order to estimate two key parameters related to particle phase state: volatility and glass transition temperature. In addition the evolution of particle size and composition will be modeled using the kinetic multi-layer model of gas-particle interaction in aerosols and clouds (KM-GAP). We will also analyze field data of SOA chemical composition and concentrations of key gases from four recent DOE-funded campaigns (HI-SCALE, GoAmazon2014/15, NPFS, BAECC). Using the molecular corridor approach and KM-GAP, our analysis will focus on quantifying the limitations on the rates of reactive and non-reactive (reversible) uptake of organics, ammonia and amines into particles. The second objective of this proposal is to develop a model representation and evaluate the effects of phase state and water content on formation, growth, and chemical transformation of SOA in a regional climate and air quality model (e.g., WRF-Chem) and to compare model predictions with ARM field measurements. Spatial distribution and temporal evolution of aerosol water content, glass transition temperature and SOA phase state will be modeled for campaign-long simulations. The impacts of phase state and water content on SOA lifecycle will be evaluated in a regional scale with the ultimate goal of reducing the uncertainty of SOA representation in regional climate and air quality predictions.
Related Publications
Maclean A, Y Li, G Crescenzo, N Smith, V Karydis, A Tsimpidi, C Butenhoff, C Faiola, J Lelieveld, S Nizkorodov, M Shiraiwa, and A Bertram. 2021. "Global Distribution of the Phase State and Mixing Times within Secondary Organic Aerosol Particles in the Troposphere Based on Room-Temperature Viscosity Measurements." ACS Earth and Space Chemistry, 5(12), 10.1021/acsearthspacechem.1c00296.
Smith N, J Montoya-Aguilera, D Dabdub, and S Nizkorodov. 2021. "Effect of Humidity on the Reactive Uptake of Ammonia and Dimethylamine by Nitrogen-Containing Secondary Organic Aerosol." Atmosphere, 12(11), 10.3390/atmos12111502.
Li Y, A Carlton, and M Shiraiwa. 2021. "Diurnal and Seasonal Variations in the Phase State of Secondary Organic Aerosol Material over the Contiguous US Simulated in CMAQ." ACS Earth and Space Chemistry, 5(8), 10.1021/acsearthspacechem.1c00094.
Galeazzo T, R Valorso, Y Li, M Camredon, B Aumont, and M Shiraiwa. 2021. "Estimation of secondary organic aerosol viscosity from explicit modeling of gas-phase oxidation of isoprene and α-pinene." Atmospheric Chemistry and Physics, 21(13), 10.5194/acp-21-10199-2021.
Shiraiwa M and U Pöschl. 2021. "Mass accommodation and gas–particle partitioning in secondary organic aerosols: dependence on diffusivity, volatility, particle-phase reactions, and penetration depth." Atmospheric Chemistry and Physics, 21(3), 10.5194/acp-21-1565-2021.
Kasparoglu S, Y Li, M Shiraiwa, and M Petters. 2021. "Toward closure between predicted and observed particle viscosity over a wide range of temperatures and relative humidity." Atmospheric Chemistry and Physics, 21(2), 10.5194/acp-21-1127-2021.
Smith N, G Crescenzo, Y Huang, A Hettiyadura, K Siemens, Y Li, C Faiola, A Laskin, M Shiraiwa, A Bertram, and S Nizkorodov. 2021. "Viscosity and liquid–liquid phase separation in healthy and stressed plant SOA." Environmental Science: Atmospheres, 1(3), 10.1039/D0EA00020E.
He Y, A Akherati, T Nah, N Ng, L Garofalo, D Farmer, M Shiraiwa, R Zaveri, C Cappa, J Pierce, and S Jathar. 2021. "Particle Size Distribution Dynamics Can Help Constrain the Phase State of Secondary Organic Aerosol." Environmental Science & Technology, 55(3), 10.1021/acs.est.0c05796.
Maclean A, N Smith, Y Li, Y Huang, A Hettiyadura, G Crescenzo, M Shiraiwa, A Laskin, S Nizkorodov, and A Bertram. 2021. "Humidity-Dependent Viscosity of Secondary Organic Aerosol from Ozonolysis of β-Caryophyllene: Measurements, Predictions, and Implications." ACS Earth and Space Chemistry, 5(2), 10.1021/acsearthspacechem.0c00296.
Li Y, D Day, H Stark, J Jimenez, and M Shiraiwa. 2020. "Predictions of the glass transition temperature and viscosity of organic aerosols from volatility distributions." Atmospheric Chemistry and Physics, 20(13), 10.5194/acp-20-8103-2020.
Song M, A Maclean, Y Huang, N Smith, S Blair, J Laskin, A Laskin, W DeRieux, Y Li, M Shiraiwa, S Nizkorodov, and A Bertram. 2019. "Liquid–liquid phase separation and viscosity within secondary organic aerosol generated from diesel fuel vapors." Atmospheric Chemistry and Physics, 19(19), 10.5194/acp-19-12515-2019.
Evoy E, A Maclean, G Rovelli, Y Li, A Tsimpidi, V Karydis, S Kamal, J Lelieveld, M Shiraiwa, J Reid, and A Bertram. 2019. "Predictions of diffusion rates of large organic molecules in secondary organic aerosols using the Stokes–Einstein and fractional Stokes–Einstein relations." Atmospheric Chemistry and Physics, 19(15), 10.5194/acp-19-10073-2019.
DeRieux W, P Lakey, Y Chu, C Chan, H Glicker, J Smith, A Zuend, and M Shiraiwa. 2019. "Effects of Phase State and Phase Separation on Dimethylamine Uptake of Ammonium Sulfate and Ammonium Sulfate–Sucrose Mixed Particles." ACS Earth and Space Chemistry, 3(7), 10.1021/acsearthspacechem.9b00142.
Li Y and M Shiraiwa. 2019. "Timescales of secondary organic aerosols to reach equilibrium at various temperatures and relative humidities." Atmospheric Chemistry and Physics, 19(9), 10.5194/acp-19-5959-2019.
Li Y and M Shiraiwa. 2018. Molecular Corridors, Volatility and Particle Phase State in Secondary Organic Aerosols. In Multiphase Environmental Chemistry in the Atmosphere, pp. 209-244. Ed. by Sherri W. Hunt, A. Laskin, and S. Nizkorodov, American Chemical Society.
DeRieux W, Y Li, P Lin, J Laskin, A Laskin, A Bertram, S Nizkorodov, and M Shiraiwa. 2018. "Predicting the glass transition temperature and viscosity of secondary organic material using molecular composition." Atmospheric Chemistry and Physics, 18(9), 10.5194/acp-18-6331-2018.
Mu Q, M Shiraiwa, M Octaviani, N Ma, A Ding, H Su, G Lammel, U Pöschl, and Y Cheng. 2018. "Temperature effect on phase state and reactivity controls atmospheric multiphase chemistry and transport of PAHs." Science Advances, 4(3), 10.1126/sciadv.aap7314.
Hinks M, J Montoya-Aguilera, L Ellison, P Lin, A Laskin, J Laskin, M Shiraiwa, D Dabdub, and S Nizkorodov. 2018. "Effect of relative humidity on the composition of secondary organic aerosol from the oxidation of toluene." Atmospheric Chemistry and Physics, 18(3), 10.5194/acp-18-1643-2018.