Global variability in atmospheric new particle formation mechanisms.

A key challenge in aerosol pollution studies and climate change assessment is to understand how atmospheric aerosol particles are initially formed1,2. Although new particle formation (NPF) mechanisms have been described at specific sites3-6, in most regions, such mechanisms remain uncertain to a large extent because of the limited ability of atmospheric models to simulate critical NPF processes1,7. Here we synthesize molecular-level experiments to develop comprehensive representations of 11 NPF mechanisms and the complex chemical transformation of precursor gases in a fully coupled global climate model. Combined simulations and observations show that the dominant NPF mechanisms are distinct worldwide and vary with region and altitude. Previously neglected or underrepresented mechanisms involving organics, amines, iodine oxoacids and HNO3 probably dominate NPF in most regions with high concentrations of aerosols or large aerosol radiative forcing; such regions include oceanic and human-polluted continental boundary layers, as well as the upper troposphere over rainforests and Asian monsoon regions. These underrepresented mechanisms also play notable roles in other areas, such as the upper troposphere of the Pacific and Atlantic oceans. Accordingly, NPF accounts for different fractions (10-80%) of the nuclei on which cloud forms at 0.5% supersaturation over various regions in the lower troposphere. The comprehensive simulation of global NPF mechanisms can help improve estimation and source attribution of the climate effects of aerosols.

Secondary Organic Aerosol Formation from the Photooxidation of Aromatic Ketone Intermediate Volatile Organic Compounds.

Oxygenated aromatics are substantial secondary organic aerosol (SOA) precursors, such as benzyl alcohol and phenolic compounds. Aromatic ketone intermediate volatile organic compounds (IVOCs), as a subclass of oxygenated aromatics, were found in anthropogenic source emissions and may contribute to SOA formation. However, the SOA yields and formation pathways of aromatic ketone IVOCs remain unknown. In this study, the photooxidations of aromatic ketone IVOCs in the absence and presence of NOx were studied in an oxidation flow reactor, and the particle- and gas-phase oxidation products were measured. The maximum SOA yields of benzophenone and 1,2-diphenylethanone are 0.24 and 0.33-0.35, respectively, relatively high among oxygenated aromatics. The SOA yields in the presence of NOx are 2-3 times higher than those in the absence of NOx in the late stage of oxidation. As the photooxidation proceeds, H/C of SOA slightly increases with O/C, and a greater amount of more-oxidized ring-retaining products exists in the particle phase in the presence of NOx. Based on gas-phase products and possible reaction pathways, functionalization of benzoic acid via the phenolic pathway is favored in the presence of NOx. Thus, our study highlights the significant SOA formation from aromatic ketone IVOCs, especially in the presence of NOx during long-time photooxidation.

Global Anthropogenic Emissions of Full-Volatility Organic Compounds.

Traditional global emission inventories classify primary organic emissions into nonvolatile organic carbon and volatile organic compounds (VOCs), excluding intermediate-volatility and semivolatile organic compounds (IVOCs and SVOCs, respectively), which are important precursors of secondary organic aerosols. This study establishes the first global anthropogenic full-volatility organic emission inventory with chemically speciated or volatility-binned emission factors. The emissions of extremely low/low-volatility organic compounds (xLVOCs), SVOCs, IVOCs, and VOCs in 2015 were 13.2, 10.1, 23.3, and 120.5 Mt, respectively. The full-volatility framework fills a gap of 18.5 Mt I/S/xLVOCs compared with the traditional framework. Volatile chemical products (VCPs), domestic combustion, and on-road transportation sources were dominant contributors to full-volatility emissions, accounting for 30, 30, and 12%, respectively. The VCP and on-road transportation sectors were the main contributors to IVOCs and VOCs. The key emitting regions included Africa, India, Southeast Asia, China, Europe, and the United States, among which China, Europe, and the United States emitted higher proportions of IVOCs and VOCs owing to the use of cleaner fuel in domestic combustion and more intense emissions from VCPs and on-road transportation activities. The findings contribute to a better understanding of the impact of organic emissions on global air pollution and climate change.