Secondary Organic Aerosol Formation of Fleet Vehicle Emissions in China: Potential Seasonality of Spatial Distributions.

Vehicle emissions are an important source of urban particular matter. To investigate the secondary organic aerosol (SOA) formation potential of real-world vehicle emissions, we exposed on-road air in Beijing to hydroxyl radicals generated in an oxidation flow reactor (OFR) under high-NOx conditions on-board a mobile laboratory and characterized SOA and their precursors with a suite of state-of-the-art instrumentation. The OFR produced 10-170 µg m-3 of SOA with a maximum SOA formation potential of 39-50 µg m-3 ppmv-1 CO that occurred following an integrated OH exposure of (1.3-2.0) × 1011 molecules cm-3 s. The results indicate relatively shorter photochemical ages for maximum SOA production than previous OFR results obtained under low-NOx conditions. Such timescales represent the balance of functionalization and fragmentation, possibly resulting in different spatial distributions of SOA in different seasons as the oxidant level changes. The detected precursors may explain as much as 13% of the observed SOA with the remaining plausibly contributed by the oxidation of undetected intermediate-volatility organic compounds. Extrapolation of the results suggests an annual SOA production rate of 0.78 Tg yr-1 from mobile gasoline sources in China, highlighting the importance of effective regulation of gaseous vehicular precursors to improve air quality in the future.

Secondary Production of Gaseous Nitrated Phenols in Polluted Urban Environments.

Nitrated phenols (NPs) are important atmospheric pollutants that affect air quality, radiation, and health. The recent development of the time-of-flight chemical ionization mass spectrometer (ToF-CIMS) allows quantitative online measurements of NPs for a better understanding of their sources and environmental impacts. Herein, we deployed nitrate ions as reagent ions in the ToF-CIMS and quantified six classes of gaseous NPs in Beijing. The concentrations of NPs are in the range of 1 to 520 ng m-3. Nitrophenol (NPh) has the greatest mean concentration. Dinitrophenol (DNP) shows the greatest haze-to-clean concentration ratio, which may be associated with aqueous production. The high concentrations and distinct diurnal profiles of NPs indicate a strong secondary formation to overweigh losses, driven by high emissions of precursors, strong oxidative capacity, and high NOx levels. The budget analysis on the basis of our measurements and box-model calculations suggest a minor role of the photolysis of NPs (<1 ppb h-1) in producing OH radicals. NPs therefore cannot explain the underestimated OH production in urban environments. Discrepancies between these results and the laboratory measurements of the NP photolysis rates indicate the need for further studies aimed at understanding the production and losses of NPs in polluted urban environments.

Potentially Important Contribution of Gas-Phase Oxidation of Naphthalene and Methylnaphthalene to Secondary Organic Aerosol during Haze Events in Beijing.

Naphthalene (Nap) and methylnaphthalene (MN) are the most abundant polycyclic aromatic hydrocarbons (PAHs) in atmosphere and have been proposed to be important precursors of anthropogenic secondary organic aerosol (SOA) derived from laboratory chamber experiments. In this study, atmospheric Nap/MN and their gas-phase photooxidation products were quantified by a Proton Transfer Reaction-Quadrupole interface Time-of-Flight Mass Spectrometer (PTR-QiTOF) during the 2016 winter in Beijing. Phthalic anhydride, a late generation product from Nap under high-NO x conditions, appeared to be more prominent than 2-formylcinnamaldehyde (early generation product), possibly due to more sufficient oxidation during the haze. 1,2-Phthalic acid (1,2-PhA), the hydrated form of phthalic anhydride, was capable of partitioning into aerosol phase and served as a tracer to explore the contribution of Nap to ambient SOA. The measured fraction in particle phase ( Fp) of 1,2-PhA averaged at 73 ± 13% with OA mass loadings of 52.5-87.8 µg/m3, lower than the value predicted by the absorptive partitioning model (100%). Using tracer product-based and precursor consumption-based methods, 2-ring PAHs (Nap and MN) were estimated to produce 14.9% (an upper limit) of the SOA formed in the afternoon during the wintertime haze, suggesting a comparable contribution of Nap and MN with monocyclic-aromatics on urban SOA formation.