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The impact of biomass burning and aqueous-phase processing on air quality: A multi-year source apportionment study in the Po Valley, Italy

2020, Paglione, Marco, Gilardoni, Stefania, Rinaldi, Matteo, Decesari, Stefano, Zanca, Nicola, Sandrini, Silvia, Giulianelli, Lara, Bacco, Dimitri, Ferrari, Silvia, Poluzzi, Vanes, Scotto, Fabiana, Trentini, Arianna, Poulain, Laurent, Herrmann, Hartmut, Wiedensohler, Alfred, Canonaco, Francesco, Prévôt, André S.H., Massoli, Paola, Carbone, Claudio, Facchini, Maria Cristina, Fuzzi, Sandro

The Po Valley (Italy) is a well-known air quality hotspot characterized by particulate matter (PM) levels well above the limit set by the European Air Quality Directive and by the World Health Organization, especially during the colder season. In the framework of Emilia-Romagna regional project "Supersito", the southern Po Valley submicron aerosol chemical composition was characterized by means of high-resolution aerosol mass spectroscopy (HR-AMS) with the specific aim of organic aerosol (OA) characterization and source apportionment. Eight intensive observation periods (IOPs) were carried out over 4 years (from 2011 to 2014) at two different sites (Bologna, BO, urban background, and San Pietro Capofiume, SPC, rural background), to characterize the spatial variability and seasonality of the OA sources, with a special focus on the cold season. On the multi-year basis of the study, the AMS observations show that OA accounts for averages of 45 ± 8 % (ranging from 33 % to 58 %) and 46 ± 7 % (ranging from 36 % to 50 %) of the total non-refractory submicron particle mass (PM1-NR) at the urban and rural sites, respectively. Primary organic aerosol (POA) comprises biomass burning (23±13 % of OA) and fossil fuel (12±7 %) contributions with a marked seasonality in concentration. As expected, the biomass burning contribution to POA is more significant at the rural site (urban / rural concentration ratio of 0.67), but it is also an important source of POA at the urban site during the cold season, with contributions ranging from 14 % to 38 % of the total OA mass. Secondary organic aerosol (SOA) contributes to OA mass to a much larger extent than POA at both sites throughout the year (69 ± 16 % and 83 ± 16 % at the urban and rural sites, respectively), with important implications for public health. Within the secondary fraction of OA, the measurements highlight the importance of biomass burning aging products during the cold season, even at the urban background site. This biomass burning SOA fraction represents 14 %-44 % of the total OA mass in the cold season, indicating that in this region a major contribution of combustion sources to PM mass is mediated by environmental conditions and atmospheric reactivity. © 2020 Author(s).

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Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VII-Criegee intermediates

2020, Cox, R. Anthony, Ammann, Markus, Crowley, John N., Herrmann, Hartmut, Jenkin, Michael E., Faye McNeill, V., Mellouki, Abdelwahid, Troe, Jürgen, Wallington, Timothy J.

This article, the seventh in the series, presents kinetic and photochemical data sheets evaluated by the IUPAC Task Group on Atmospheric Chemical Kinetic Data Evaluation. It covers an extension of the gas-phase and photochemical reactions related to Criegee intermediates previously published in Atmospheric Chemistry and Physics (ACP) in 2006 and implemented on the IUPAC website up to 2020. The article consists of an introduction, description of laboratory measurements, a discussion of rate coefficients for reactions of O3 with alkenes producing Criegee intermediates, rate coefficients of unimolecular and bimolecular reactions and photochemical data for reactions of Criegee intermediates, and an overview of the atmospheric chemistry of Criegee intermediates. Summary tables of the recommended kinetic and mechanistic parameters for the evaluated reactions are provided. Data sheets summarizing information upon which the recommendations are based are given in two files, provided as a Supplement to this article. © Author(s) 2020.

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Chemical characteristics of cloud water and the impacts on aerosol properties at a subtropical mountain site in Hong Kong SAR

2020, Li, Tao, Wang, Zhe, Wang, Yaru, Wu, Chen, Liang, Yiheng, Xia, Men, Yu, Chuan, Yun, Hui, Wang, Weihao, Wang, Yan, Guo, Jia, Herrmann, Hartmut, Wang, Tao

To investigate the cloud water chemistry and the effects of cloud processing on aerosol properties, comprehensive field observations of cloud water, aerosols, and gasphase species were conducted at a mountaintop site in Hong Kong SAR in October and November 2016. The chemical composition of cloud water including water-soluble ions, dissolved organic matter (DOM), carbonyl compounds (refer to aldehydes and acetone), carboxylic acids, and trace metals was quantified. The measured cloud water was very acidic with a mean pH of 3.63, as the ammonium (174 μeq L-1) was insufficient for neutralizing the dominant sulfate (231 μeq L-1) and nitrate (160 μeq L-1). Substantial DOM (9.3 mgC L-1) was found in cloud water, with carbonyl compounds and carboxylic acids accounting for 18% and 6% in carbon molar concentrations, respectively. Different from previous observations, concentrations of methylglyoxal (19.1 μM; μM is equal to μmol L-1) and glyoxal (6.72 μM) were higher than that of formaldehyde (1.59 μM). The partitioning of carbonyls between cloud water and the gas phase was also investigated. The measured aqueous fractions of dicarbonyls were comparable to the theoretical estimations, while significant aqueous-phase supersaturation was found for less soluble monocarbonyls. Both organics and sulfate were significantly produced in cloud water, and the aqueous formation of organics was more enhanced by photochemistry and under less acidic conditions. Moreover, elevated sulfate and organics were measured in the cloudprocessed aerosols, and they were expected to contribute largely to the increase in droplet-mode aerosol mass fraction. This study demonstrates the significant role of clouds in altering the chemical compositions and physical properties of aerosols via scavenging and aqueous chemical processing, providing valuable information about gas-cloud-aerosol interactions in subtropical and coastal regions. © 2020 Author(s). This work is distributed under the Creative Commons Attribution 4.0 License.