Modeling Volatility-Based Aerosol Phase State Predictions in the Amazon Rainforest

Journal Article · Wed Sep 29 00:00:00 EDT 2021 · ACS Earth and Space Chemistry

DOI:https://doi.org/10.1021/acsearthspacechem.1c00255· OSTI ID:1830503

Rasool, Fnu Quazi Ziaur  ^[1]; Shrivastava, ManishKumar B.  ^[1]; Octaviani, Mega ^[1]; Zhao, Bin ^[1]; Gaudet, Brian J.  ^[1]; Liu, Ying  ^[1]

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1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Organic aerosol (OA) is a complex matrix of various constituents—fresh (primary organic aerosols—POA) and aged via oxidation (secondary organic aerosols—SOA), generated from biogenic, anthropogenic, and biomass burning sources. The viscosity of OA can be critical in influencing new particle formation, reactive uptake processes that impact evaporation-growth kinetics, and the lifetime of particles in the atmosphere. We report this work utilizes a well-defined relationship between volatility and viscosity for pure compounds, which we incorporated within the Weather Research and Forecasting Model coupled to chemistry (WRF-Chem) to simulate the phase state and viscosity of bulk OA during the dry-to-wet transition season (September–October) in the Amazon rainforest during 2014. Our simulations indicate spatial and temporal heterogeneity in aerosol phase state often not captured by global-scale models. We show the strong role of water associated with organic aerosol ($$w_s$$) as the dominant factor that can be used to quantitatively estimate OA viscosity. Analysis of WRF-Chem simulations across the entire atmospheric column indicates a strong inverse log-linear relationship between $$w_s$$ and OA viscosity with a correlation coefficient approaching 1, in the background and biomass burning-influenced conditions. At high altitudes where relative humidity (RH) and temperatures are low, our simulations indicate that OA exists in a semisolid-/solid-like phase state, consistent with previous studies. OA hygroscopicity is strongly correlated (ca. –0.8) with OA viscosity at RH ca. 30–50%, but this RH range is found mostly at low OA concentrations and the middle troposphere (ca. 6–10 km altitudes) in our simulated domain. OA hygroscopicity is uncorrelated with viscosity at higher-RH (near surface) and lower-RH (upper troposphere) regimes. At the urban site near surface, where day–night differences in RH are significant, RH is found to drive the phase state. At the background forested site near surface, where day–night RH differences are small, biomass burning-influenced OA is semisolid and a significant OA associated with background conditions is liquid-like. Simulations indicate a long tail of OA viscosity frequency distributions extending in the semisolid/solid regimes over background biogenic-influenced conditions due to the role of low-volatility OA components such as monoterpene oxidation products.

• Research Organization: Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
• Sponsoring Organization: USDOE Office of Science (SC), Biological and Environmental Research (BER)
• Grant/Contract Number: AC05-76RL01830
• OSTI ID: 1830503
• Report Number(s): PNNL-SA-164372
• Journal Information: ACS Earth and Space Chemistry, Vol. 5, Issue 10; ISSN 2472-3452
• Publisher: American Chemical Society (ACS)
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
aerosol dynamics
aerosol phase state
viscosity
volatility
atmospheric modeling
tropospheric chemistry
aerosol water content
biomass burning
phase state
secondary organic aerosols
glass-transition temperature
phase transitions
water uptake by organic aerosols
Amazon rainforest