Dual effect of anthropogenic emissions on the formation of biogenicSOA

Abstract

Abstract. The fraction of gasoline direct injection (GDI) vehicles comprising the total vehicle pool is projected to increase in the future. However, thorough knowledge about the influence of GDI engines on important atmospheric chemistry processes is missing—from their contribution to secondary organic aerosol (SOA) precursor emissions, SOA formation, and potential role in biogenic-anthropogenic interactions. The objectives of this study were to 1) characterize emissions from modern GDI vehicle and investigate their role in SOA formation chemistry and 2) investigate biogenic-anthropogenic interactions related to SOA formation from a mixture of GDI vehicle emissions and a model biogenic compound, α-pinene. Specifically, we studied SOA formation from modern GDI vehicle emissions during the constant load driving. In this study we show that SOA formation from GDI vehicle emissions was observed in each experiment. VOCs measured with the PTR-ToF-MS could account for 19−42% of total SOA mass generated in each experiments. This suggests there were lower volatility intermediate-VOCs (IVOCs) and semi-VOCs (SVOCs) in the GDI exhaust that likely contributed to SOA production but were not detected with the instrumentation used in this study. This study also demonstrates that two distinct mechanisms caused by anthropogenic emissions suppress α-pinene SOA mass yield. The first suppressing effect was the presence of NOx. This mechanism is consistent with previous reports demonstrating suppression of biogenic SOA formation in the presence of anthropogenic emissions. Our results imply that the second suppressing effect was the presence of anthropogenic gas-phase species that suppressed biogenic SOA formation by changing the gas-phase chemistry of α-pinene. This change in oxidation pathways led to formation of α-pinene oxidation products that most likely do not have vapor pressures low enough to partition into the particle phase. Overall, the presence of gasoline vehicle exhaust caused more than 50\u2009% suppression in α-pinene SOA mass yield compared to the α-pinene SOA mass yield measured in the absence of an anthropogenic influence.