The chemistry of the formation of nitrogen-containing compounds in secondary organic aerosols and their impact on aerosol optical properties
Final Report Abstract
One of the main open questions regarding organic compounds in atmospheric chemistry today is related to the formation of light-absorbing compounds and the occurrence of socalled brown carbon. Ambient secondary organic aerosols have been assumed to not absorb solar radiation and to have a cooling effect on climate for decades. However, it is now generally accepted that a continuum of light-absorbing carbonaceous species is present in these fine particles. In this project, we studied the formation of nitrogencontaining compounds in organic aerosols. In systematic experiments, reactions between dicarbonyl compounds and reduced inorganic and organic amine components were found to be efficient pathways for the formation of a variety of nitrogen-containing heterocyclic products, which can absorb light in the actinic flux region of the UV/Vis spectrum. These products appear to be common structural motifs of secondary brown carbon and could potentially affect the absorption properties of secondary organic aerosols in the atmosphere. As of now, they have not been included in corresponding model simulations of aerosol-induced radiative forcing. Furthermore, mixtures of different dicarbonyl species in ammonium sulfate solutions yielded light-absorbing cross-reaction products. These synergistic effects of cross-reactions on secondary brown carbon formation were observed for mixtures of small carbonyl compounds, e.g., acetylacetone and acetaldehyde forming a strongly absorbing dihydropyridine. Mixtures of small carbonyl compounds with an atmospherically relevant monoterpene ozonolysis intermediate, e.g., the second-generation ozonolysis product of limonene ketolimononaldehyde, also showed synergistic effects for brown carbon formation due to cross-reaction products. Our results indicate that secondary brown carbon formation via the imine pathway may be a ubiquitous process with potential effects on particle properties such as absorbance, viscosity, and particle growth. Future research may focus the identification of suitable marker substances for dicarbonyl amine reactions in ambient aerosol samples and SOA particle heterogeneous chemistry induced by the photosensitization of nitrogencontaining brown carbon constituents.
Publications
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Computational Study of the Effect of Glyoxal–Sulfate Clustering on the Henry’s Law Coefficient of Glyoxal, J. Phys. Chem. A 2015, 119, 4509–4514
T. Kurtén, J. Elm, N. L. Prisle, K. V. Mikkelsen, C. J. Kampf, E. M. Waxman, R. Volkamer
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Protein Cross-Linking and Oligomerization through Dityrosine Formation upon Exposure to Ozone, Environ. Sci. Technol. 2015, 49, 10859–10866
C. J. Kampf, F. Liu, K. Reinmuth-Selzle, T. Berkemeier, H. Meusel, M. Shiraiwa, U. Pöschl
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Bioaerosols in the Earth system: Climate, health, and ecosystem interactions, Atmos. Res. 2016, 182, 346–376
J. Fröhlich-Nowoisky, C. J. Kampf, B. Weber, J. A. Huffman, C. Pöhlker, M. O. Andreae, N. Lang-Yona, S. M. Burrows, S. S. Gunthe, W. Elbert, H. Su, P. Hoor, E. Thines, T. Hoffmann, V. R. Després, U. Pöschl
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Hydroxyl radicals from secondary organic aerosol decomposition in water, Atmos. Chem. Phys. 2016, 16, 1761–1771
H. Tong, A. M. Arangio, P. S. J. Lakey, T. Berkemeier, F. Liu, C. J. Kampf, W. H. Brune, U. Pöschl, M. Shiraiwa
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Metaproteomic analysis of atmospheric aerosol samples, Anal. Bioanal. Chem. 2016, 408, 6337–6348
F. Liu, S. Lai, K. Reinmuth-Selzle, J. F. Scheel, J. Fröhlich-Nowoisky, V. R. Després, T. Hoffmann, U. Pöschl, C. J. Kampf
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Secondary brown carbon formation via the dicarbonyl imine pathway: nitrogen heterocycle formation and synergistic effects, Phys Chem Chem Phys 2016, 18, 18353–18364
C. J. Kampf, A. Filippi, C. Zuth, T. Hoffmann and T. Opatz
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Air Pollution and Climate Change Effects on Allergies in the Anthropocene: Abundance, Interaction, and Modification of Allergens and Adjuvants, Environ. Sci. Technol. 2017, 51, 4419–4141
K. Reinmuth-Selzle, C. J. Kampf, K. Lucas, N. Lang-Yona, J. Fröhlich-Nowoisky, M. Shiraiwa, P. S. Lakey, S. Lai, F. Liu, A. T. Kunert, K. Ziegler, F. Shen, R. Sgarbanti, B. Weber, I. Bellinghausen, J. Saloga, M. G. Weller, A. Duschl, D. Schuppan, U. Pöschl
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Atmospheric protein chemistry influenced by anthropogenic air pollutants: nitration and oligomerization upon exposure to ozone and nitrogen dioxide, Faraday Discuss. 2017, 200, 413–427
F. Liu, P. S. J. Lakey, T. Berkemeier, H. Tong, A. T. Kunert, H. Meusel, H. Su, Y. Cheng, J. Fröhlich-Nowoisky, S. Lai, M. G. Weller, M. Shiraiwa, U. Pöschl, C. J. Kampf
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Light-induced protein nitration and degradation with HONO emission, Atmos. Chem. Phys. 2017, 17, 11819–11833
H. Meusel, Y. Elshobany, U. Kuhn, T. Bartels-Rausch, K. Reinmuth-Selzle, C. J. Kampf, G. Li, X. Wang, J. Lelieveld, U. Pöschl, T. Hoffmann, H. Su, M. Ammann, Y. Cheng
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Reactive Oxygen species formed in aqueous mixtures of secondary organic aerosols and mineral dust influencing cloud chemistry and public health in the Anthropocene, Faraday Discuss. 2017, 200, 251–270
H. Tong, P. S. J. Lakey, A. M. Arangio, J. Socorro, C. J. Kampf, T. Berkemeier, W. H. Brune, U. Pöschl, M. Shiraiwa
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Release of free amino acids upon oxidation of peptides and proteins by hydroxyl radicals, Anal. Bioanal. Chem. 2017, 409, 2411–2420
F. Liu, S. Lai, H. Tong, P. S. J. Lakey, M. Shiraiwa, M. G. Weller, U. Pöschl, C. J. Kampf
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Simultaneous determination of nitrated and oligomerized proteins by size exclusion high-performance liquid chromatography coupled to photodiode array detection, J. Chrom. A 2017, 1495, 76–82
F. Liu, K. Reinmuth-Selzle, S. Lai, M. G. Weller, U. Pöschl, C. J. Kampf
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Fresh water, marine and terrestrial cyanobacteria display distinct allergen characteristics, Sci. Total Environ. 2018, 612, 767–774
Lang-Yona, A. T. Kunert, L. Vogel, C. J. Kampf, I. Bellinghausen, J. Saloga, A. Schenk, K. Ziegler, K. Lucas, D. Schuppan, U. Pöschl, B. Weber, J. Fröhlich- Nowoisky
