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1. Morphology of Organic/Inorganic Aerosol with Varying Seed Particle Water Content

   https://doi.org/10.1021/acsearthspacechem.3c00202  

   Tackman, Emma C.; Higgins, Devon N.; Johnston, Murray V.; Freedman, Miriam Arak (September 2023, ACS Earth and Space Chemistry)

   The morphology of mixed organic/inorganic particles can strongly influence the physicochemical properties of aerosols but remains relatively less examined in particle formation studies. The morphologies of inorganic seed particles grown with either -pinene or limonene secondary organic aerosol (SOA) generated in a flow tube reactor were found to depend on initial seed particle water content. Effloresced and deliquesced ammonium sulfate seed particles were generated at low relative humidity (<15% RH, dry) and high relative humidity (~60% RH, wet) and were also coated with secondary organic material under low growth and high growth conditions. Particles were dried and analyzed using SMPS and TEM for diameter and substrate-induced diameter changes and for the prevalence of phase separation for organic-coated particles. Effloresced inorganic seed particle diameters generally increased after impaction, whereas deliquesced inorganic seed particles had smaller differences in diameter, although they appeared morphologically similar to the effloresced seed particles. Differences in the changes to diameter for deliquesced seed particles suggest crystal restructuring with RH cycling. SOA-coated particles showed negative diameter changes for low organic growth, although wet-seeded organic particles changed by larger magnitudes compared to dry-seeded organic particles. High organic growth gave wide ranging diameter percent differences for both dry- and wet-seeded samples. Wet-seeded particles with organic coatings occasionally showed a textured morphology unseen in the coated particles with dry seeds. Using a flow tube reactor with a combination of spectrometry and microscopy techniques allows for insights into the dependence of aerosol particle morphology on formation parameters for two seed conditions and two secondary organic precursors. 

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2. Viscosity and liquid–liquid phase separation in healthy and stressed plant SOA

   https://doi.org/10.1039/d0ea00020e  

   Smith, Natalie R.; Crescenzo, Giuseppe V.; Huang, Yuanzhou; Hettiyadura, Anusha P.; Siemens, Kyla; Li, Ying; Faiola, Celia L.; Laskin, Alexander; Shiraiwa, Manabu; Bertram, Allan K.; et al (January 2021, Environmental Science: Atmospheres)

   null (Ed.)

   Molecular composition, viscosity, and liquid–liquid phase separation (LLPS) were investigated for secondary organic aerosol (SOA) derived from synthetic mixtures of volatile organic compounds (VOCs) representing emission profiles for Scots pine trees under healthy and aphid-herbivory stress conditions. Model “healthy plant SOA” and “stressed plant SOA” were generated in a 5 m 3 environmental smog chamber by photooxidation of the mixtures at 50% relative humidity (RH). SOA from photooxidation of α-pinene was also prepared for comparison. Molecular composition was determined with high resolution mass spectrometry, viscosity was determined with the poke-flow technique, and liquid–liquid phase separation was investigated with optical microscopy. The stressed plant SOA had increased abundance of higher molecular weight species, reflecting a greater fraction of sesquiterpenes in the stressed VOC mixture compared to the healthy plant VOC mixture. LLPS occurred in both the healthy and stressed plant SOA; however, stressed plant SOA exhibited phase separation over a broader humidity range than healthy plant SOA, with LLPS persisting down to 23 ± 11% RH. At RH ≤25%, both stressed and healthy plant SOA viscosity exceeded 10 8 Pa s, a value similar to that of tar pitch. At 40% and 50% RH, stressed plant SOA had the highest viscosity, followed by healthy plant SOA and then α-pinene SOA in descending order. The observed peak abundances in the mass spectra were also used to estimate the SOA viscosity as a function of RH and volatility. The predicted viscosity of the healthy plant SOA was lower than that of the stressed plant SOA driven by both the higher glass transition temperatures and lower hygroscopicity of the organic molecules making up stressed plant SOA. These findings suggest that plant stress influences the physicochemical properties of biogenic SOA. Furthermore, a complex mixture of VOCs resulted in a higher SOA viscosity compared to SOA generated from α-pinene alone at ≥25% RH, highlighting the importance of studying properties of SOA generated from more realistic multi-component VOC mixtures. 

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3. Influence of seed aerosol surface area and oxidation rate on vapor wall deposition and SOA mass yields: a case study with α-pinene ozonolysis

   https://doi.org/10.5194/acp-16-9361-2016  

   Nah, Theodora; McVay, Renee C.; Zhang, Xuan; Boyd, Christopher M.; Seinfeld, John H.; Ng, Nga L. (January 2016, Atmospheric Chemistry and Physics)

   Laboratory chambers, invaluable in atmospheric chemistry and aerosol formation studies, are subject to particle and vapor wall deposition, processes that need to be accounted for in order to accurately determine secondary organic aerosol (SOA) mass yields. Although particle wall deposition is reasonably well understood and usually accounted for, vapor wall deposition is less so. The effects of vapor wall deposition on SOA mass yields in chamber experiments can be constrained experimentally by increasing the seed aerosol surface area to promote the preferential condensation of SOA-forming vapors onto seed aerosol. Here, we study the influence of seed aerosol surface area and oxidation rate on SOA formation in α-pinene ozonolysis. The observations are analyzed using a coupled vapor–particle dynamics model to interpret the roles of gas–particle partitioning (quasi-equilibrium vs. kinetically limited SOA growth) and α-pinene oxidation rate in influencing vapor wall deposition. We find that the SOA growth rate and mass yields are independent of seed surface area within the range of seed surface area concentrations used in this study. This behavior arises when the condensation of SOA-forming vapors is dominated by quasi-equilibrium growth. Faster α-pinene oxidation rates and higher SOA mass yields are observed at increasing O₃ concentrations for the same initial α-pinene concentration. When the α-pinene oxidation rate increases relative to vapor wall deposition, rapidly produced SOA-forming oxidation products condense more readily onto seed aerosol particles, resulting in higher SOA mass yields. Our results indicate that the extent to which vapor wall deposition affects SOA mass yields depends on the particular volatility organic compound system and can be mitigated through the use of excess oxidant concentrations. 

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4. The Influence of Absolute Mass Loading of Secondary Organic Aerosols on Their Phase State

   https://doi.org/10.3390/atmos9040131  

   S.Jain, K.B. Fischer (April 2018, Atmosphere)

   Absolute secondary organic aerosol (SOA) mass loading (CSOA) is a key parameter in determining partitioning of semi- and intermediate volatility compounds to the particle phase. Its impact on the phase state of SOA, however, has remained largely unexplored. In this study, systematic laboratory chamber measurements were performed to elucidate the influence of CSOA, ranging from 0.2 to 160 µg m−3, on the phase state of SOA formed by ozonolysis of various precursors, including α-pinene, limonene, cis-3-hexenyl acetate (CHA) and cis-3-hexen-1-ol (HXL). A previously established method to estimate SOA bounce factor (BF, a surrogate for particle viscosity) was utilized to infer particle viscosity as a function of CSOA. Results show that under nominally identical conditions, the maximum BF decreases by approximately 30% at higher CSOA, suggesting a more liquid phase state. With the exception of HXL-SOA (which acted as the negative control), the phase state for all studied SOA precursors varied as a function of CSOA. Furthermore, the BF was found to be the maximum when SOA particle distributions reached a geometric mean particle diameter of 50–60 nm. Experimental results indicate that CSOA is an important parameter impacting the phase state of SOA, reinforcing recent findings that extrapolation of experiments not conducted at atmospherically relevant SOA levels may not yield results that are relevant to the natural environment. 

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5. Secondary brown carbon from photooxidation of 1-methylnaphthalene and longifolene

   https://doi.org/10.6086/D1R38Z  

   Bahreini, Roya (January 2022, Dryad)

   An improved understanding of the optical properties of secondary organic aerosol (SOA) particles is needed to better predict their climate impacts. Here, SOA was produced by reacting 1-methylnaphthalene or longifolene with hydroxyl radicals (OH) under variable ammonia (NH3), nitrogen oxide (NOx), and relative humidity (RH) conditions. In the presence of NH3 and NOx, longifolene-derived aerosols had relatively high single scattering albedo (SSA) values and low absorption coefficients at 375 nm independent of RH, suggesting that the longifolene SOA is mostly scattering. In 1-methylnaphthalene experiments, the resulting SSA and SOA mass absorption coefficient (MACorg) values suggest the formation of light-absorbing SOA, and the addition of high NOx and high NH3 enhanced the SOA absorption. Under intermediate-NOx dry conditions, the MACorg values increased from 0.13 m2 g−1 in NH3-free conditions to 0.28 m2 g−1 in high-NH3 conditions. Under high-NH3 conditions, the MACorg value further increased to 0.36 m2 g−1 with an increase in RH. Under dry high-NOx conditions, the MACorg value increased from 0.42 to 0.67 m2 g−1 with the addition of NH3, while with elevated RH, the MACorg value reached 0.70 m2 g−1. The time series of MACorg showed increasing trends only in the presence of NH3. Composition analysis of SOA suggests that organonitrates, nitroorganics, and other nitrogen-containing organic compounds (NOCs) are potential chromophores in the 1-methylnaphthalene SOA. Significant formation of NOCs was observed in the presence of high-NOx and NH3 and was enhanced under elevated RH. The data have been collected in an environmental chamber, oxidizing 30-100 ppbv of 1-methylnaphthalene and 70-100 ppbv of longifolene under different levels of nitrogen oxides, ammonia, and relative humidity. Microphysical properties (size distribution and absorption and scattering coefficients) of SOA along with its composition were monitored throughout the experiment. Submitted data include the time series of the calculated mass absorption coefficient and single scattering albedo at 375 nm, derived real and imaginary components of the refractive index, organic nitrate to organic ratio, and organic and nitrate mass concentrations. The data have been analyzed using Wavemetrics Igor Pro, specifically the software written specifically to analyze the data obtained from Aerodyne's aerosol mass spectrometers (i.e., Squirrel and Pika). Other calculations were also carried out in Igor Pro. More details are provided in the related manuscripts. Please see README file. 

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