The daytime oxidation of biogenic hydrocarbons is attributed to both OH radicals and O3, while nighttime chemistry is dominated by the reaction with O3 and NO3 radicals. Here, the diurnal pattern of Secondary Organic Aerosol (SOA) originating from biogenic hydrocarbons was intensively evaluated under varying environmental conditions (temperature, humidity, sunlight intensity, NOx levels, and seed conditions) by using the UNIfied Partitioning Aerosol phase Reaction (UNIPAR) model, which comprises multiphase gas-particle partitioning and in-particle chemistry. The oxidized products of three different hydrocarbons (isoprene, α-pinene, and β-caryophyllene) were predicted by using near explicit gas mechanisms for four different oxidation paths (OH, O3, NO3, and O(3P)) during day and night. The gas mechanisms implemented the Master Chemical Mechanism (MCM v3.3.1), the reactions that formed low volatility products via peroxy radical (RO2) autoxidation, and self- and cross-reactions of nitrate-origin RO2. In the model, oxygenated products were then classified into volatility-reactivity base lumping species, which were dynamically constructed under varying NOx levels and aging scales. To increase feasibility, the UNIPAR model that equipped mathematical equations for stoichiometric coefficients and physicochemical parameters of lumping species was integrated with the SAPRC gas mechanism. The predictability of the UNIPAR model was demonstrated by simulating chamber-generated SOA data under varying environments day and night. Overall, the SOA simulation decoupled to each oxidation path indicated that the nighttime isoprene SOA formation was dominated by the NO3-driven oxidation, regardless of NOx levels. However, the oxidation path to produce the nighttime α-pinene SOA gradually transited from the NO3-initiated reaction to ozonolysis as NOx levels decreased. For daytime SOA formation, both isoprene and α-pinene were dominated by the OH-radical initiated oxidation. The contribution of the O(3P) path to all biogenic SOA formation was negligible in daytime. Sunlight during daytime promotes the decomposition of oxidized products via photolysis and thus, reduces SOA yields. Nighttime α-pinene SOA yields were significantly higher than daytime SOA yields, although the nighttime α-pinene SOA yields gradually decreased with decreasing NOx levels. For isoprene, nighttime chemistry yielded higher SOA mass than daytime at the higher NOx level (isoprene/NOx > 5 ppbC/ppb). The daytime isoprene oxidation at the low NOx level formed epoxy-diols that significantly contributed SOA formation via heterogeneous chemistry. For isoprene and α-pinene, daytime SOA yields gradually increased with decreasing NOx levels. The daytime SOA produced more highly oxidized multifunctional products and thus, it was generally more sensitive to the aqueous reactions than the nighttime SOA. β-Caryophyllene, which rapidly oxidized and produced SOA with high yields, showed a relatively small variation in SOA yields from changes in environmental conditions (i.e., NOx levels, seed conditions, and diurnal pattern), and its SOA formation was mainly attributed to ozonolysis day and night. To mimic the nighttime α-pinene SOA formation under the polluted urban atmosphere, α-pinene SOA formation was simulated in the presence of gasoline fuel. The simulation suggested the growth of α-pinene SOA in the presence of gasoline fuel gas by the enhancement of the ozonolysis path under the excess amount of ozone, which is typical in urban air. We concluded that the oxidation of the biogenic hydrocarbon with O3 or NO3 radicals is a source to produce a sizable amount of nocturnal SOA, despite of the low emission at night.
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Hygroscopicity of Internally Mixed Ammonium Sulfate and Secondary Organic Aerosol Particles Formed at Low and High Relative Humidity
Volatile organic matter that is suspended in the atmosphere such as α-Pinene and β-caryophyllene undergoes aging processes, as well as chemical and photooxidation reactions to create secondary organic aerosol (SOA), which can influence the indirect effect of aerosol particles and the radiative budget. The presence and impact of water vapor and ammonium sulfate (ubiquitous species in the atmosphere) on the hygroscopicity and CCN activity of SOA has not been well characterized. In this research, three water-uptake measurement methods: cavity ring-down spectroscopy (CRD), humidified tandem differential mobility analysis (HTDMA), and cloud condensation nuclei counting (CCNC) were employed to study the hygroscopicity of α-pinene and β-caryophyllene SOA formed under dark ozonolysis. We observed the changes in water uptake of SOA in the absence and presence of water vapor at ~70 % RH and ammonium sulfate seeds. Measured hygroscopicity was represented by the single hygroscopicity parameter (κ). κ of α-pinene SOA was measured to be 0.04 and can increase up to 0.19 in the presence of water vapor and ammonium sulfate. β-caryophyllene SOA exhibited non-hygroscopic properties with κ values that were effectively 0. It is proposed that a difference in the viscosity and hydrophobicity of the SOA may be the primary factor that leads to changes in hygroscopicity.
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- Award ID(s):
- 1723920
- NSF-PAR ID:
- 10312325
- Date Published:
- Journal Name:
- Environmental Science: Atmospheres
- ISSN:
- 2634-3606
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D1EA00069A
