CCN activity and organic hygroscopicity of aerosols downwind of an urban region in central Amazonia: seasonal and diel variations and impact of anthropogenic emissions

作者：Thalman Ryan; de Sa Suzane S; Palm Brett B; Barbosa Henrique M J; Poehlker Mira L; Alexander M Lizabeth; Brito Joel; Carbone Samara; Castillo Paulo; Day Douglas A; Kuang Chongai; Manzi Antonio; Ng Nga Lee; Sedlacek Arthur J III; Souza Rodrigo; Springston Stephen; Watson Thomas; Poehlker Christopher; Poeschl Ulrich; Andreae Meinrat O; Artaxo Paulo; Jimenez Jose L; Martin Scot T; Wang Jian

来源：Atmospheric Chemistry and Physics, 2017, 17(19): 11779-11801.

DOI：10.5194/acp-17-11779-2017

During the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) campaign, sizeresolved cloud condensation nuclei (CCN) spectra were characterized at a research site (T3) 60 km downwind of the city of Manaus, Brazil, in central Amazonia for 1 year (12 March 2014 to 3 March 2015). Particle hygroscopicity ((CCN)-C-kappa) and mixing state were derived from the size-resolved CCN spectra, and the hygroscopicity of the organic component of the aerosol (kappa(org)) was then calculated from (CCN)-C-kappa and concurrent chemical composition measurements. The annual average (CCN)-C-kappa increased from 0.13 at 75 nm to 0.17 at 171 nm, and the increase was largely due to an increase in sulfate volume fraction. During both wet and dry seasons, (CCN)-C-kappa, kappa(org), and particle composition under background con-ditions exhibited essentially no diel variations. The constant kappa(org) of similar to 0 : 15 is consistent with the largely uniform and high O:C value (similar to 0 : 8), indicating that the aerosols under background conditions are dominated by the aged regional aerosol particles consisting of highly oxygenated organic compounds. For air masses strongly influenced by urban pollution and/or local biomass burning, lower values of kappa(org) and organic O: C atomic ratio were observed during night, due to accumulation of freshly emitted particles, dominated by primary organic aerosol (POA) with low hygroscopicity, within a shallow nocturnal boundary layer. The O: C, kappa(org), and (CCN)-C-kappa increased from the early morning hours and peaked around noon, driven by the formation and aging of secondary organic aerosol (SOA) and dilution of POA emissions into boundary layer, while the development of the boundary layer, which leads to mixing with aged particles from the residual layer aloft, likely also contributed to the increases. The hygroscopicities associated with individual organic factors, derived from PMF (positive matrix factorization) analysis of AMS (aerosol mass spectrometry) spectra, were estimated through multivariable linear regression. For the SOA factors, the variation of the kappa value with O: C agrees well with the linear relationship reported from earlier laboratory studies of SOA hygroscopicity. On the other hand, the variation in O: C of ambient aerosol organics is largely driven by the variation in the volume fractions of POA and SOA factors, which have very different O: C values. As POA factors have hygroscopicity values well below the linear relationship between SOA hygroscopicity and O: C, mixtures with different POA and SOA fractions exhibit a steeper slope for the increase in kappa(org) with O: C, as observed during this and earlier field studies. This finding helps better understand and reconcile the differences in the relationships between kappa(org) and O: C observed in laboratory and field studies, therefore providing a basis for improved parameterization in global models, especially in a tropical context.

• 出版日期2017-10-5