Articles | Volume 16, issue 23
https://doi.org/10.5194/acp-16-15425-2016
© Author(s) 2016. This work is distributed under
the Creative Commons Attribution 3.0 License.
the Creative Commons Attribution 3.0 License.
https://doi.org/10.5194/acp-16-15425-2016
© Author(s) 2016. This work is distributed under
the Creative Commons Attribution 3.0 License.
the Creative Commons Attribution 3.0 License.
The acid-catalyzed hydrolysis of an α-pinene-derived organic nitrate: kinetics, products, reaction mechanisms, and atmospheric impact
Joel D. Rindelaub
CORRESPONDING AUTHOR
Department of Chemistry, Purdue University, West Lafayette, IN 47907, USA
Carlos H. Borca
Department of Chemistry, Purdue University, West Lafayette, IN 47907, USA
Matthew A. Hostetler
Department of Chemistry, Purdue University, West Lafayette, IN 47907, USA
Jonathan H. Slade
Department of Chemistry, Purdue University, West Lafayette, IN 47907, USA
Mark A. Lipton
Department of Chemistry, Purdue University, West Lafayette, IN 47907, USA
Lyudmila V. Slipchenko
Department of Chemistry, Purdue University, West Lafayette, IN 47907, USA
Paul B. Shepson
CORRESPONDING AUTHOR
Department of Chemistry, Purdue University, West Lafayette, IN 47907, USA
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Wanmin Gong, Stephen R. Beagley, Kenjiro Toyota, Henrik Skov, Jesper Heile Christensen, Alex Lupu, Diane Pendlebury, Junhua Zhang, Ulas Im, Yugo Kanaya, Alfonso Saiz-Lopez, Roberto Sommariva, Peter Effertz, John W. Halfacre, Nis Jepsen, Rigel Kivi, Theodore K. Koenig, Katrin Müller, Claus Nordstrøm, Irina Petropavlovskikh, Paul B. Shepson, William R. Simpson, Sverre Solberg, Ralf M. Staebler, David W. Tarasick, Roeland Van Malderen, and Mika Vestenius
Atmos. Chem. Phys., 25, 8355–8405, https://doi.org/10.5194/acp-25-8355-2025, https://doi.org/10.5194/acp-25-8355-2025, 2025
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This study showed that the springtime O3 depletion plays a critical role in driving the surface O3 seasonal cycle in the central Arctic. The O3 depletion events, while occurring most notably within the lowest few hundred metres above the Arctic Ocean, can induce a 5–7 % loss in the pan-Arctic tropospheric O3 burden during springtime. The study also found enhancements in O3 and NOy (mostly peroxyacetyl nitrate) concentrations in the Arctic due to northern boreal wildfires, particularly at higher altitudes.
Yugo Kanaya, Roberto Sommariva, Alfonso Saiz-Lopez, Andrea Mazzeo, Theodore K. Koenig, Kaori Kawana, James E. Johnson, Aurélie Colomb, Pierre Tulet, Suzie Molloy, Ian E. Galbally, Rainer Volkamer, Anoop Mahajan, John W. Halfacre, Paul B. Shepson, Julia Schmale, Hélène Angot, Byron Blomquist, Matthew D. Shupe, Detlev Helmig, Junsu Gil, Meehye Lee, Sean C. Coburn, Ivan Ortega, Gao Chen, James Lee, Kenneth C. Aikin, David D. Parrish, John S. Holloway, Thomas B. Ryerson, Ilana B. Pollack, Eric J. Williams, Brian M. Lerner, Andrew J. Weinheimer, Teresa Campos, Frank M. Flocke, J. Ryan Spackman, Ilann Bourgeois, Jeff Peischl, Chelsea R. Thompson, Ralf M. Staebler, Amir A. Aliabadi, Wanmin Gong, Roeland Van Malderen, Anne M. Thompson, Ryan M. Stauffer, Debra E. Kollonige, Juan Carlos Gómez Martin, Masatomo Fujiwara, Katie Read, Matthew Rowlinson, Keiichi Sato, Junichi Kurokawa, Yoko Iwamoto, Fumikazu Taketani, Hisahiro Takashima, Monica Navarro Comas, Marios Panagi, and Martin G. Schultz
Earth Syst. Sci. Data Discuss., https://doi.org/10.5194/essd-2024-566, https://doi.org/10.5194/essd-2024-566, 2025
Revised manuscript accepted for ESSD
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The first comprehensive dataset of tropospheric ozone over oceans/polar regions is presented, including 77 ship/buoy and 48 aircraft campaign observations (1977–2022, 0–5000 m altitude), supplemented by ozonesonde and surface data. Air masses isolated from land for 72+ hours are systematically selected as essentially oceanic. Among the 11 global regions, they show daytime decreases of 10–16% in the tropics, while near-zero depletions are rare, unlike in the Arctic, implying different mechanisms.
Nathaniel Brockway, Peter K. Peterson, Katja Bigge, Kristian D. Hajny, Paul B. Shepson, Kerri A. Pratt, Jose D. Fuentes, Tim Starn, Robert Kaeser, Brian H. Stirm, and William R. Simpson
Atmos. Chem. Phys., 24, 23–40, https://doi.org/10.5194/acp-24-23-2024, https://doi.org/10.5194/acp-24-23-2024, 2024
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Bromine monoxide (BrO) strongly affects atmospheric chemistry in the springtime Arctic, yet there are still many uncertainties around its sources and recycling, particularly in the context of a rapidly changing Arctic. In this study, we observed BrO as a function of altitude above the Alaskan Arctic. We found that BrO was often most concentrated near the ground, confirming the ability of snow to produce and recycle reactive bromine, and identified four common vertical distributions of BrO.
Brandon Bottorff, Michelle M. Lew, Youngjun Woo, Pamela Rickly, Matthew D. Rollings, Benjamin Deming, Daniel C. Anderson, Ezra Wood, Hariprasad D. Alwe, Dylan B. Millet, Andrew Weinheimer, Geoff Tyndall, John Ortega, Sebastien Dusanter, Thierry Leonardis, James Flynn, Matt Erickson, Sergio Alvarez, Jean C. Rivera-Rios, Joshua D. Shutter, Frank Keutsch, Detlev Helmig, Wei Wang, Hannah M. Allen, Johnathan H. Slade, Paul B. Shepson, Steven Bertman, and Philip S. Stevens
Atmos. Chem. Phys., 23, 10287–10311, https://doi.org/10.5194/acp-23-10287-2023, https://doi.org/10.5194/acp-23-10287-2023, 2023
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The hydroxyl (OH), hydroperoxy (HO2), and organic peroxy (RO2) radicals play important roles in atmospheric chemistry and have significant air quality implications. Here, we compare measurements of OH, HO2, and total peroxy radicals (XO2) made in a remote forest in Michigan, USA, to predictions from a series of chemical models. Lower measured radical concentrations suggest that the models may be missing an important radical sink and overestimating the rate of ozone production in this forest.
Qianjie Chen, Jessica A. Mirrielees, Sham Thanekar, Nicole A. Loeb, Rachel M. Kirpes, Lucia M. Upchurch, Anna J. Barget, Nurun Nahar Lata, Angela R. W. Raso, Stephen M. McNamara, Swarup China, Patricia K. Quinn, Andrew P. Ault, Aaron Kennedy, Paul B. Shepson, Jose D. Fuentes, and Kerri A. Pratt
Atmos. Chem. Phys., 22, 15263–15285, https://doi.org/10.5194/acp-22-15263-2022, https://doi.org/10.5194/acp-22-15263-2022, 2022
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During a spring field campaign in the coastal Arctic, ultrafine particles were enhanced during high wind speeds, and coarse-mode particles were reduced during blowing snow. Calculated periods blowing snow were overpredicted compared to observations. Sea spray aerosols produced by sea ice leads affected the composition of aerosols and snowpack. An improved understanding of aerosol emissions from leads and blowing snow is critical for predicting the future climate of the rapidly warming Arctic.
Dandan Wei, Hariprasad D. Alwe, Dylan B. Millet, Brandon Bottorff, Michelle Lew, Philip S. Stevens, Joshua D. Shutter, Joshua L. Cox, Frank N. Keutsch, Qianwen Shi, Sarah C. Kavassalis, Jennifer G. Murphy, Krystal T. Vasquez, Hannah M. Allen, Eric Praske, John D. Crounse, Paul O. Wennberg, Paul B. Shepson, Alexander A. T. Bui, Henry W. Wallace, Robert J. Griffin, Nathaniel W. May, Megan Connor, Jonathan H. Slade, Kerri A. Pratt, Ezra C. Wood, Mathew Rollings, Benjamin L. Deming, Daniel C. Anderson, and Allison L. Steiner
Geosci. Model Dev., 14, 6309–6329, https://doi.org/10.5194/gmd-14-6309-2021, https://doi.org/10.5194/gmd-14-6309-2021, 2021
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Over the past decade, understanding of isoprene oxidation has improved, and proper representation of isoprene oxidation and isoprene-derived SOA (iSOA) formation in canopy–chemistry models is now recognized to be important for an accurate understanding of forest–atmosphere exchange. The updated FORCAsT version 2.0 improves the estimation of some isoprene oxidation products and is one of the few canopy models currently capable of simulating SOA formation from monoterpenes and isoprene.
Taylor S. Jones, Jonathan E. Franklin, Jia Chen, Florian Dietrich, Kristian D. Hajny, Johannes C. Paetzold, Adrian Wenzel, Conor Gately, Elaine Gottlieb, Harrison Parker, Manvendra Dubey, Frank Hase, Paul B. Shepson, Levi H. Mielke, and Steven C. Wofsy
Atmos. Chem. Phys., 21, 13131–13147, https://doi.org/10.5194/acp-21-13131-2021, https://doi.org/10.5194/acp-21-13131-2021, 2021
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Methane emissions from leaks in natural gas pipes are often a large source in urban areas, but they are difficult to measure on a city-wide scale. Here we use an array of innovative methane sensors distributed around the city of Indianapolis and a new method of combining their data with an atmospheric model to accurately determine the magnitude of these emissions, which are about 70 % larger than predicted. This method can serve as a framework for cities trying to account for their emissions.
Ana C. Morales, Thilina Jayarathne, Jonathan H. Slade, Alexander Laskin, and Paul B. Shepson
Atmos. Chem. Phys., 21, 129–145, https://doi.org/10.5194/acp-21-129-2021, https://doi.org/10.5194/acp-21-129-2021, 2021
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Organic nitrates formed from the oxidation of biogenic volatile organic compounds impact both ozone and particulate matter as they remove nitrogen oxides, but they represent important aerosol precursors. We conducted a series of reaction chamber experiments that quantified the total organic nitrate and secondary organic aerosol yield from the OH-radical-initiated oxidation of ocimene, and also measured their hydrolysis lifetimes in the aqueous phase, as a function of pH.
Olivia E. Salmon, Lisa R. Welp, Michael E. Baldwin, Kristian D. Hajny, Brian H. Stirm, and Paul B. Shepson
Atmos. Chem. Phys., 19, 11525–11543, https://doi.org/10.5194/acp-19-11525-2019, https://doi.org/10.5194/acp-19-11525-2019, 2019
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We conducted airborne vertical profile measurements of water vapor stable isotopes to examine how boundary layer, cloud, and mixing processes influence the vertical structure of deuterium excess in the lower troposphere. We discuss reasons our observations are consistent with water vapor isotope theory on some days and not others. Deuterium excess may be useful for understanding complex processes occurring at the top of the boundary layer, including cloud formation, evaporation, and air mixing.
John W. Halfacre, Paul B. Shepson, and Kerri A. Pratt
Atmos. Chem. Phys., 19, 4917–4931, https://doi.org/10.5194/acp-19-4917-2019, https://doi.org/10.5194/acp-19-4917-2019, 2019
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In this study, we found that a chemical called hydroxyl radical can help create chlorine, bromine, and iodine (i.e., halogens) from acidic frozen imitation seawater. Even more halogens are created if we also add ozone. This result helps our understanding of how halogens are released from the frozen Arctic ice and snow into the atmosphere, where they alter the atmosphere's oxidation ability.
Shino Toma, Steve Bertman, Christopher Groff, Fulizi Xiong, Paul B. Shepson, Paul Romer, Kaitlin Duffey, Paul Wooldridge, Ronald Cohen, Karsten Baumann, Eric Edgerton, Abigail R. Koss, Joost de Gouw, Allen Goldstein, Weiwei Hu, and Jose L. Jimenez
Atmos. Chem. Phys., 19, 1867–1880, https://doi.org/10.5194/acp-19-1867-2019, https://doi.org/10.5194/acp-19-1867-2019, 2019
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Acyl peroxy nitrates (APN) were measured near the ground in Alabama using GC in summer 2013 to study biosphere–atmosphere interactions. APN were lower than measured in the SE USA over the past 2 decades. Historical data showed APN in 2013 was limited by NOx and production was dominated by biogenic precursors more than in the past. Isoprene-derived MPAN correlated with isoprene hydroxynitrates as NOx-dependent products. MPAN varied with aerosol growth, but not with N-containing particles.
William R. Simpson, Peter K. Peterson, Udo Frieß, Holger Sihler, Johannes Lampel, Ulrich Platt, Chris Moore, Kerri Pratt, Paul Shepson, John Halfacre, and Son V. Nghiem
Atmos. Chem. Phys., 17, 9291–9309, https://doi.org/10.5194/acp-17-9291-2017, https://doi.org/10.5194/acp-17-9291-2017, 2017
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We investigated Arctic atmospheric bromine chemistry during March–April 2012 to improve understanding of the role of sea ice and cracks in sea ice (leads) in this phenomenon. We find that leads vertically redistribute reactive bromine but that open/re-freezing leads are not major direct reactive halogen sources. Surface ozone depletion affects the vertical distribution and amount of reactive halogens, and aerosol particles are necessary but not sufficient to maintain reactive bromine aloft.
Jonathan H. Slade, Chloé de Perre, Linda Lee, and Paul B. Shepson
Atmos. Chem. Phys., 17, 8635–8650, https://doi.org/10.5194/acp-17-8635-2017, https://doi.org/10.5194/acp-17-8635-2017, 2017
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This study provides new insight into the oxidation of polyolefinic monoterpenes and the dependence of the formation and yields of organic nitrates (ON) and secondary organic aerosol (SOA) on hydrocarbon structure. Here we have elucidated the ON, hydroxy nitrate, and SOA yields from the NO3 oxidation of γ-terpinene, a potentially relevant nighttime ON precursor in the Midwestern US. The results advance our understanding of the chemistry that influences NOx, O3 production, and aerosol formation.
Peter K. Peterson, Denis Pöhler, Holger Sihler, Johannes Zielcke, Stephan General, Udo Frieß, Ulrich Platt, William R. Simpson, Son V. Nghiem, Paul B. Shepson, Brian H. Stirm, Suresh Dhaniyala, Thomas Wagner, Dana R. Caulton, Jose D. Fuentes, and Kerri A. Pratt
Atmos. Chem. Phys., 17, 7567–7579, https://doi.org/10.5194/acp-17-7567-2017, https://doi.org/10.5194/acp-17-7567-2017, 2017
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High-spatial-resolution aircraft measurements in the Arctic showed the sustained transport of reactive bromine in a lofted layer via heterogeneous reactions on aerosol particles. This process provides an explanation for free tropospheric reactive bromine and the significant spatial extent of satellite-observed bromine monoxide. The knowledge gained herein improves our understanding of the fate and transport of atmospheric pollutants in the Arctic.
Chelsea R. Thompson, Paul B. Shepson, Jin Liao, L. Greg Huey, Chris Cantrell, Frank Flocke, and John Orlando
Atmos. Chem. Phys., 17, 3401–3421, https://doi.org/10.5194/acp-17-3401-2017, https://doi.org/10.5194/acp-17-3401-2017, 2017
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The generally accepted mechanism leading to ozone depletion events in the Arctic assumes efficient gas-phase recycling of bromine atoms, such that the rate of ozone depletion has often been estimated as the rate that Br atoms regenerate through gas-phase BrO + BrO and BrO + ClO reactions. Using a large suite of data from the OASIS2009 campaign, our modeling results show that the gas-phase regeneration of Br is less efficient than expected and that heterogeneous recycling on surfaces is critical.
Luping Su, Edward G. Patton, Jordi Vilà-Guerau de Arellano, Alex B. Guenther, Lisa Kaser, Bin Yuan, Fulizi Xiong, Paul B. Shepson, Li Zhang, David O. Miller, William H. Brune, Karsten Baumann, Eric Edgerton, Andrew Weinheimer, Pawel K. Misztal, Jeong-Hoo Park, Allen H. Goldstein, Kate M. Skog, Frank N. Keutsch, and John E. Mak
Atmos. Chem. Phys., 16, 7725–7741, https://doi.org/10.5194/acp-16-7725-2016, https://doi.org/10.5194/acp-16-7725-2016, 2016
Jenny A. Fisher, Daniel J. Jacob, Katherine R. Travis, Patrick S. Kim, Eloise A. Marais, Christopher Chan Miller, Karen Yu, Lei Zhu, Robert M. Yantosca, Melissa P. Sulprizio, Jingqiu Mao, Paul O. Wennberg, John D. Crounse, Alex P. Teng, Tran B. Nguyen, Jason M. St. Clair, Ronald C. Cohen, Paul Romer, Benjamin A. Nault, Paul J. Wooldridge, Jose L. Jimenez, Pedro Campuzano-Jost, Douglas A. Day, Weiwei Hu, Paul B. Shepson, Fulizi Xiong, Donald R. Blake, Allen H. Goldstein, Pawel K. Misztal, Thomas F. Hanisco, Glenn M. Wolfe, Thomas B. Ryerson, Armin Wisthaler, and Tomas Mikoviny
Atmos. Chem. Phys., 16, 5969–5991, https://doi.org/10.5194/acp-16-5969-2016, https://doi.org/10.5194/acp-16-5969-2016, 2016
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We use new airborne and ground-based observations from two summer 2013 campaigns in the southeastern US, interpreted with a chemical transport model, to understand the impact of isoprene and monoterpene chemistry on the atmospheric NOx budget via production of organic nitrates (RONO2). We find that a diversity of species contribute to observed RONO2. Our work implies that the NOx sink to RONO2 production is only sensitive to NOx emissions in regions where they are already low.
Fulizi Xiong, Carlos H. Borca, Lyudmila V. Slipchenko, and Paul B. Shepson
Atmos. Chem. Phys., 16, 5595–5610, https://doi.org/10.5194/acp-16-5595-2016, https://doi.org/10.5194/acp-16-5595-2016, 2016
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Here we report on a detailed study of the photochemistry and fate of a nitrooxy enal that is produced from the reaction of NO3 with isoprene. We synthesized the 4,1-nitrooxy enal, purified it, and measured the O3 and OH reaction rate constants, and determined the atmospheric photodissociation rate constant for specified radiation conditions. The determined fast photolysis rate and high reactivity toward OH lead to a lifetime of less than 1 hour, with photolysis being a dominant daytime sink.
F. Xiong, K. M. McAvey, K. A. Pratt, C. J. Groff, M. A. Hostetler, M. A. Lipton, T. K. Starn, J. V. Seeley, S. B. Bertman, A. P. Teng, J. D. Crounse, T. B. Nguyen, P. O. Wennberg, P. K. Misztal, A. H. Goldstein, A. B. Guenther, A. R. Koss, K. F. Olson, J. A. de Gouw, K. Baumann, E. S. Edgerton, P. A. Feiner, L. Zhang, D. O. Miller, W. H. Brune, and P. B. Shepson
Atmos. Chem. Phys., 15, 11257–11272, https://doi.org/10.5194/acp-15-11257-2015, https://doi.org/10.5194/acp-15-11257-2015, 2015
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Hydroxynitrates from isoprene oxidation were quantified both in the laboratory and through field studies. The yield of hydroxynitrates 9(+4/-3)% derived from chamber experiments was applied in a zero-dimensional model to simulate the production and loss of isoprene hydroxynitrates in an ambient environment during the 2013 Southern Oxidant and Aerosol Study (SOAS). NOx was determined to be the limiting factor for the formation of isoprene hydroxynitrates during SOAS.
K. D. Custard, C. R. Thompson, K. A. Pratt, P B. Shepson, J. Liao, L. G. Huey, J. J. Orlando, A. J. Weinheimer, E. Apel, S. R. Hall, F. Flocke, L. Mauldin, R. S. Hornbrook, D. Pöhler, S. General, J. Zielcke, W. R. Simpson, U. Platt, A. Fried, P. Weibring, B. C. Sive, K. Ullmann, C. Cantrell, D. J. Knapp, and D. D. Montzka
Atmos. Chem. Phys., 15, 10799–10809, https://doi.org/10.5194/acp-15-10799-2015, https://doi.org/10.5194/acp-15-10799-2015, 2015
J. H. Slade, R. Thalman, J. Wang, and D. A. Knopf
Atmos. Chem. Phys., 15, 10183–10201, https://doi.org/10.5194/acp-15-10183-2015, https://doi.org/10.5194/acp-15-10183-2015, 2015
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Aerosol particles undergo chemical modification during atmospheric transport due to reactions with trace gas species such as OH radicals affecting cloud formation and, thus, prediction of climate. Here, the cloud formation potential of surrogate biomass burning aerosol (BBA) is studied as a function of particle composition and OH exposure. We find that OH oxidation can alter the cloud formation potential of BBA, but its significance depends on the available water-soluble particulate material.
C. R. Thompson, P. B. Shepson, J. Liao, L. G. Huey, E. C. Apel, C. A. Cantrell, F. Flocke, J. Orlando, A. Fried, S. R. Hall, R. S. Hornbrook, D. J. Knapp, R. L. Mauldin III, D. D. Montzka, B. C. Sive, K. Ullmann, P. Weibring, and A. Weinheimer
Atmos. Chem. Phys., 15, 9651–9679, https://doi.org/10.5194/acp-15-9651-2015, https://doi.org/10.5194/acp-15-9651-2015, 2015
P. K. Peterson, W. R. Simpson, K. A. Pratt, P. B. Shepson, U. Frieß, J. Zielcke, U. Platt, S. J. Walsh, and S. V. Nghiem
Atmos. Chem. Phys., 15, 2119–2137, https://doi.org/10.5194/acp-15-2119-2015, https://doi.org/10.5194/acp-15-2119-2015, 2015
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We developed methods to measure the vertical distribution of bromine monoxide, a gas that oxidizes pollutants, above sea ice based upon MAX-DOAS observations from Barrow, Alaska, and find that atmospheric stability exerts a strong control on BrO's vertical distribution. Specifically, more stable (temperature inversion) situations result in BrO being closer to the ground while more neutral (not inverted) atmospheres allow BrO to ascend further aloft and grow to larger column abundance.
S. General, D. Pöhler, H. Sihler, N. Bobrowski, U. Frieß, J. Zielcke, M. Horbanski, P. B. Shepson, B. H. Stirm, W. R. Simpson, K. Weber, C. Fischer, and U. Platt
Atmos. Meas. Tech., 7, 3459–3485, https://doi.org/10.5194/amt-7-3459-2014, https://doi.org/10.5194/amt-7-3459-2014, 2014
M. O. L. Cambaliza, P. B. Shepson, D. R. Caulton, B. Stirm, D. Samarov, K. R. Gurney, J. Turnbull, K. J. Davis, A. Possolo, A. Karion, C. Sweeney, B. Moser, A. Hendricks, T. Lauvaux, K. Mays, J. Whetstone, J. Huang, I. Razlivanov, N. L. Miles, and S. J. Richardson
Atmos. Chem. Phys., 14, 9029–9050, https://doi.org/10.5194/acp-14-9029-2014, https://doi.org/10.5194/acp-14-9029-2014, 2014
J. W. Halfacre, T. N. Knepp, P. B. Shepson, C. R. Thompson, K. A. Pratt, B. Li, P. K. Peterson, S. J. Walsh, W. R. Simpson, P. A. Matrai, J. W. Bottenheim, S. Netcheva, D. K. Perovich, and A. Richter
Atmos. Chem. Phys., 14, 4875–4894, https://doi.org/10.5194/acp-14-4875-2014, https://doi.org/10.5194/acp-14-4875-2014, 2014
J. D. Rindelaub, K. M. McAvey, and P. B. Shepson
Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acpd-14-3301-2014, https://doi.org/10.5194/acpd-14-3301-2014, 2014
Revised manuscript not accepted
S. M. Griffith, R. F. Hansen, S. Dusanter, P. S. Stevens, M. Alaghmand, S. B. Bertman, M. A. Carroll, M. Erickson, M. Galloway, N. Grossberg, J. Hottle, J. Hou, B. T. Jobson, A. Kammrath, F. N. Keutsch, B. L. Lefer, L. H. Mielke, A. O'Brien, P. B. Shepson, M. Thurlow, W. Wallace, N. Zhang, and X. L. Zhou
Atmos. Chem. Phys., 13, 5403–5423, https://doi.org/10.5194/acp-13-5403-2013, https://doi.org/10.5194/acp-13-5403-2013, 2013
Related subject area
Subject: Aerosols | Research Activity: Laboratory Studies | Altitude Range: Troposphere | Science Focus: Chemistry (chemical composition and reactions)
Copper accelerates photochemically induced radical chemistry of iron-containing secondary organic aerosol (SOA)
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Secondary organic aerosol formation from nitrate radical oxidation of styrene: aerosol yields, chemical composition, and hydrolysis of organic nitrates
Hydrogen peroxide photoformation in particulate matter and its contribution to S(IV) oxidation during winter in Fairbanks, Alaska
Insight into the size-resolved markers and eco-health significance of microplastics from typical sources in northwest China
Laboratory studies on the optical, physical, and chemical properties of fresh and aged biomass burning aerosols
The importance of burning conditions on the composition of domestic biomass-burning organic aerosol and the impact of atmospheric ageing
Heterogeneous phototransformation of halogenated polycyclic aromatic hydrocarbons: influencing factors, mechanisms and products
Initiation of linoleic acid autoxidation with ozone exposure in levitated aerosol particles
Measurement Report: Seasonal trends and chemical speciation of chromium (III/VI) in different fractions of urban particulate matter – a case study of Radom, Poland
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Roles of pH, ionic strength, and sulfate in the aqueous nitrate-mediated photooxidation of green leaf volatiles
The lifetimes and potential change in planetary albedo owing to the oxidation of thin surfactant organic films extracted from atmospheric aerosol by hydroxyl (OH) radicals at the air–water interface of particles
Gas-particle partitioning of m-xylene and naphthalene oxidation products: temperature and NOx influence
Surprisingly Robust Photochemistry in Subarctic Particles During Winter: Evidence from Photooxidants
Exometabolomic exploration of culturable airborne microorganisms from an urban atmosphere
Ozonolysis of primary biomass burning organic aerosol particles: Insights into reactivity and phase state
Measurement Report: Changes in ammonia emissions since the 18th century in south-eastern Europe inferred from an Elbrus (Caucasus, Russia) ice-core record
Atmospheric oxidation of 1,3-butadiene: influence of seed aerosol acidity and relative humidity on SOA composition and the production of air toxic compounds
Formation and composition of organic aerosols from the uptake of glyoxal on natural mineral dust aerosols: a laboratory study
Enhanced sulfate formation in mixed biomass burning and sea-salt interactions mediated by photosensitization: effects of chloride, nitrogen-containing compounds, and atmospheric aging
Photochemical aging of aviation emissions: transformation of chemical and physical properties of exhaust emissions from a laboratory-scale jet engine combustion chamber
Heterogeneous formation and light absorption of secondary organic aerosols from acetone photochemical reactions: remarkably enhancing effects of seeds and ammonia
Experimental observation of the impact of nanostructure on hygroscopicity and reactivity of fatty acid atmospheric aerosol proxies
Technical note: High-resolution analyses of concentrations and sizes of refractory black carbon particles deposited in northwestern Greenland over the past 350 years – Part 1: Continuous flow analysis of the SIGMA-D ice core using the wide-range Single-Particle Soot Photometer and a high-efficiency nebulizer
HOMs and SOA formation from the oxidation of α- and β-phellandrenes by NO3 radicals
Particulate emissions from cooking: emission factors, emission dynamics, and mass spectrometric analysis for different cooking methods
Nocturnal atmospheric synergistic oxidation reduces the formation of low-volatility organic compounds from biogenic emissions
The interplay between aqueous replacement reaction and the phase state of internally mixed organic/ammonium aerosols
Measurement report: The Fifth International Workshop on Ice Nucleation phase 1 (FIN-01): intercomparison of single-particle mass spectrometers
Characterization of the particle size distribution, mineralogy, and Fe mode of occurrence of dust-emitting sediments from the Mojave Desert, California, USA
Measurement report: Effects of transition metal ions on the optical properties of humic-like substances (HULIS) reveal a structural preference – a case study of PM2.5 in Beijing, China
Probing Iceland's dust-emitting sediments: particle size distribution, mineralogy, cohesion, Fe mode of occurrence, and reflectance spectra signatures
Photoenhanced sulfate formation by the heterogeneous uptake of SO2 on non-photoactive mineral dust
Comparison of water-soluble and water-insoluble organic compositions attributing to different light absorption efficiency between residential coal and biomass burning emissions
Suppressed atmospheric chemical aging of cooking organic aerosol particles in wintertime conditions
Formation and loss of light absorbance by phenolic aqueous SOA by ●OH and an organic triplet excited state
Technical Note: A technique to convert NO2 to NO2− with S(IV) and its application to measuring nitrate photolysis
Distribution, chemical, and molecular composition of high and low molecular weight humic-like substances in ambient aerosols
Desorption lifetimes and activation energies influencing gas–surface interactions and multiphase chemical kinetics
Molecular analysis of secondary organic aerosol and brown carbon from the oxidation of indole
Secondary organic aerosol formed by Euro 5 gasoline vehicle emissions: chemical composition and gas-to-particle phase partitioning
Assessment of the contribution of residential waste burning to ambient PM10 concentrations in Hungary and Romania
Source differences in the components and cytotoxicity of PM2.5 from automobile exhaust, coal combustion, and biomass burning contributing to urban aerosol toxicity
Chamber studies of OH + dimethyl sulfoxide and dimethyl disulfide: insights into the dimethyl sulfide oxidation mechanism
Low-temperature ice nucleation of sea spray and secondary marine aerosols under cirrus cloud conditions
Temperature-dependent aqueous OH kinetics of C2–C10 linear and terpenoid alcohols and diols: new rate coefficients, structure–activity relationship, and atmospheric lifetimes
A possible unaccounted source of nitrogen-containing compound formation in aerosols: amines reacting with secondary ozonides
Kevin Kilchhofer, Markus Ammann, Laura Torrent, Rico K. Y. Cheung, and Peter A. Alpert
Atmos. Chem. Phys., 25, 8061–8086, https://doi.org/10.5194/acp-25-8061-2025, https://doi.org/10.5194/acp-25-8061-2025, 2025
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Aerosol particles composed of metal complexes generate radicals as a result of photochemical reactions. The reactive species generated are hazardous to human health. We report microscopy data with particles composed of an organic proxy exposed to UV light. We found that copper influenced the reoxidation and initial iron reduction via photolysis of the complex. New model results suggest that we need to account for decreased photochemical activity and use a copper-induced reoxidation reaction.
Kathleen A. Alden, Paul Bieber, Anna J. Miller, Nicole Link, Benjamin J. Murray, and Nadine Borduas-Dedekind
Atmos. Chem. Phys., 25, 6179–6195, https://doi.org/10.5194/acp-25-6179-2025, https://doi.org/10.5194/acp-25-6179-2025, 2025
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Lignin and Snomax are surface-active macromolecules that show a relationship between increasing concentrations, decreasing surface tension, and increasing ice-nucleating ability. However, this relationship did not hold for agricultural soil extracts collected in the UK and Canada. To explain this difference, we propose that as the complexity of the sample increases, the hydrophobic interfaces in the bulk compete with the air–water interface.
Yuchen Wang, Xiang Zhang, Yuanlong Huang, Yutong Liang, and Nga L. Ng
Atmos. Chem. Phys., 25, 5215–5231, https://doi.org/10.5194/acp-25-5215-2025, https://doi.org/10.5194/acp-25-5215-2025, 2025
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This work provides the first fundamental laboratory data to evaluate SOA (secondary organic aerosol) production from styrene and NO3 chemistry. Additionally, the formation mechanisms of aromatic organic nitrates (ONs) are reported, highlighting that previously identified nitroaromatics in ambient field campaigns can be aromatic ONs. Finally, the hydrolysis lifetimes observed for ONs generated from styrene and NO3 oxidation can serve as experimentally constrained parameters for modeling hydrolysis of aromatic ONs in general.
Michael Oluwatoyin Sunday, Laura Marie Dahler Heinlein, Junwei He, Allison Moon, Sukriti Kapur, Ting Fang, Kasey C. Edwards, Fangzhou Guo, Jack Dibb, James H. Flynn III, Becky Alexander, Manabu Shiraiwa, and Cort Anastasio
Atmos. Chem. Phys., 25, 5087–5100, https://doi.org/10.5194/acp-25-5087-2025, https://doi.org/10.5194/acp-25-5087-2025, 2025
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Hydrogen peroxide (HOOH) is an important oxidant that forms atmospheric sulfate. We demonstrate that the illumination of brown carbon can rapidly form HOOH within particles, even under the low-sunlight conditions of Fairbanks, Alaska, during winter. This in-particle formation of HOOH is fast enough that it forms sulfate at significant rates. In contrast, the formation of HOOH in the gas phase during the campaign is expected to be negligible because of high NOx levels.
Liyan Liu, Hongmei Xu, Mengyun Yang, Abdullah Akhtar, Jian Sun, and Zhenxing Shen
EGUsphere, https://doi.org/10.5194/egusphere-2025-1821, https://doi.org/10.5194/egusphere-2025-1821, 2025
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Atmospheric microplastics and plasticizers can disperse into ecosystem and directly enter the human body, causing multiple adverse effects. The fingerprint markers of microplastics sources are very lacking. We examine the concentration, size distribution, eco-health risks and production of reactive oxygen species of microplastics from five typical sources, especially neglected rural sources. Our results could provide a scientific foundation for developing efficient management strategies.
Zheng Yang, Qiaoqiao Wang, Qiyuan Wang, Nan Ma, Jie Tian, Yaqing Zhou, Ge Xu, Miao Gao, Xiaoxian Zhou, Yang Zhang, Weikang Ran, Ning Yang, Jiangchuan Tao, Juan Hong, Yunfei Wu, Junji Cao, Hang Su, and Yafang Cheng
EGUsphere, https://doi.org/10.5194/egusphere-2025-1020, https://doi.org/10.5194/egusphere-2025-1020, 2025
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Our results demonstrate that the reduction in mass absorption efficiency from biomass burning is mainly driven by the decline in the imaginary part, with particle size playing a minor role. And light absorption of oxygenated BrC increases significantly with aging, but hydrocarbon-like BrC decrease over time. These results emphasize the necessity to classify BrC into different groups based on their mass absorption efficiency and atmospheric behavior in climate models.
Rhianna L. Evans, Daniel J. Bryant, Aristeidis Voliotis, Dawei Hu, Huihui Wu, Sara Aisyah Syafira, Osayomwanbor E. Oghama, Gordon McFiggans, Jacqueline F. Hamilton, and Andrew R. Rickard
Atmos. Chem. Phys., 25, 4367–4389, https://doi.org/10.5194/acp-25-4367-2025, https://doi.org/10.5194/acp-25-4367-2025, 2025
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The chemical composition of organic aerosol derived from wood-burning emissions under different burning conditions was characterised. Fresh emissions from flaming and smouldering were largely aromatic in nature, whereas upon aging the aromatic content decreased. This decrease was greater for smouldering due to the loss of toxic polyaromatic species, whereas under flaming conditions highly toxic polyaromatic species were produced. These differences present an important challenge for future policy.
Yueyao Yang, Yahui Liu, Guohua Zhu, Bingcheng Lin, Shanshan Zhang, Xin Li, Fangxi Xu, He Niu, Rong Jin, and Minghui Zheng
Atmos. Chem. Phys., 25, 3981–3994, https://doi.org/10.5194/acp-25-3981-2025, https://doi.org/10.5194/acp-25-3981-2025, 2025
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Halogenated polycyclic aromatic hydrocarbons (XPAHs) are emerging pollutants. Stability during atmospheric transformation processes is crucial for predicting their environmental fate and assessing the associated risks. Here, we conducted field studies and laboratory simulation experiments to reveal the mechanisms, influencing factors and products for XPAHs' heterogeneous phototransformation. Results revealed that the conversion of XPAHs led to a reduction in environmental risk.
Marcel Müller, Marcel Reichmuth, and Ulrich Karl Krieger
EGUsphere, https://doi.org/10.5194/egusphere-2025-1238, https://doi.org/10.5194/egusphere-2025-1238, 2025
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The initiation of autoxidation by ozonolysis was investigated on levitated linoleic acid droplets using electrodynamic balance–mass spectrometry. Exposing the droplets to ozone for one hour before switching the gas phase to air without ozone led to a shortening of the autoxidation initiation phase in comparison to experiments without ozone exposure. Results were compared to a bulk reaction model to investigate the synergistic effects of ozonolysis and autoxidation.
Monika Łożyńska, Marzena Trojanowska, Artur Molik, and Ryszard Świetlik
EGUsphere, https://doi.org/10.5194/egusphere-2025-541, https://doi.org/10.5194/egusphere-2025-541, 2025
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The assessment of chromium occurrence in particulate matter in cities: PM10, PM2.5, PM1 and PM0.25 during the calendar year was presented. The seasonality of both pseudototal chromium content and its valence speciation was examined. Seasonality of changes in Crtot and Cr(VI) concentrations was observed. Maximum in the winter season, most likely due to the greater share of fuel combustion sources. Regardless of the season, the risk levels for Radom residents were within the acceptable risk range.
Harmanjot Kaur, Stephan Thürmer, Shirin Gholami, Bruno Credidio, Florian Trinter, Debora Vasconcelos, Ricardo Marinho, Joel Pinheiro, Hendrik Bluhm, Arnaldo Naves de Brito, Gunnar Öhrwall, Bernd Winter, and Olle Björneholm
Atmos. Chem. Phys., 25, 3503–3518, https://doi.org/10.5194/acp-25-3503-2025, https://doi.org/10.5194/acp-25-3503-2025, 2025
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Understanding the surface composition of aerosols is crucial for advancing climate models. We investigated the interface of single-component and mixed aqueous solutions of atmospherically relevant carboxylic acid and alkyl-ammonium ions using liquid-jet photoelectron spectroscopy. An exponential increase in surface propensity as a function of chain length was found for the single species, and cooperative effects in the mixtures cause a further drastic increase in surface solute concentration.
Qun Zhang, Wei Zhou, Shanshan Tang, Kai Huang, Jie Fu, Zechen Yu, Yunhe Teng, Shuyi Shen, Yang Mei, Xuezhi Yang, Jianjie Fu, and Guibin Jiang
EGUsphere, https://doi.org/10.5194/egusphere-2025-1028, https://doi.org/10.5194/egusphere-2025-1028, 2025
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This article comprehensively investigates the aqueous-phase OH oxidation of benzothiazoles (BTs), common rubber additives found in urban air, through laboratory simulation experiments. BTs can rapidly degrade, leading to light absorption, high yields of sulfate, and the formation of highly oxidized and/or oligomerized organic compounds. The results reveal that aqueous-phase BTs can contribute to secondary aerosols, altering the chemical and optical properties of atmospheric particles.
Tao Cao, Cuncun Xu, Hao Chen, Jianzhong Song, Jun Li, Haiyan Song, Bin Jiang, Yin Zhong, and Ping’an Peng
EGUsphere, https://doi.org/10.5194/egusphere-2025-561, https://doi.org/10.5194/egusphere-2025-561, 2025
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This study investigated the evolution of biomass and coal combustion-derived WSOM during aqueous photochemical process. The results indicate that photochemical aging induces distinct changes in the optical and molecular properties of WSOM and more pronounced alterations were observed during ·OH photooxidation than direct photolysis. Notably, our results also demostrated that atmospheric photooxidation may represent a significant source of BC-like substances.
Yuting Lyu, Taekyu Joo, Ruihan Ma, Mark Kristan Espejo Cabello, Tianye Zhou, Shun Yeung, Cheuk Ki Wong, Yifang Gu, Yiming Qin, and Theodora Nah
EGUsphere, https://doi.org/10.5194/egusphere-2025-570, https://doi.org/10.5194/egusphere-2025-570, 2025
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We investigated the aqueous nitrate-mediated photooxidation of four green leaf volatiles (GLVs). The aqueous reaction medium conditions, dilute cloud/fog vs. concentrated aqueous aerosol conditions, governed the effects that pH, ionic strength, and sulfate have on the GLV degradation rates and aqSOA mass yields. Most notably, reactions initiated by sulfate photolysis have significant effects in aqueous aerosols, but not in cloud/fog droplets.
Rosalie H. Shepherd, Martin D. King, Andrew D. Ward, Edward J. Stuckey, Rebecca J. L. Welbourn, Neil Brough, Adam Milsom, Christian Pfrang, and Thomas Arnold
Atmos. Chem. Phys., 25, 2569–2588, https://doi.org/10.5194/acp-25-2569-2025, https://doi.org/10.5194/acp-25-2569-2025, 2025
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Thin film formation at the air–water interface from material extracted from atmospheric aerosol was demonstrated, supporting the core–shell morphology. Film thicknesses were approximately 10 Å and 17 Å for urban and remote extracts, respectively. Exposure to gas-phase OH radicals showed fast reactions and short lifetimes of around 1 h. The effect on the Earth's radiative balance indicated that removing half of the film could significantly increase the top-of-atmosphere albedo for urban films.
Marwa Shahin, Julien Kammer, Brice Temime-Roussel, and Barbara D'Anna
EGUsphere, https://doi.org/10.5194/egusphere-2025-833, https://doi.org/10.5194/egusphere-2025-833, 2025
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Air pollution and climate change are influenced by tiny airborne particles called aerosols. This study explores how pollutants from urban sources, as m-xylene and naphthalene, form new particles in the atmosphere under different conditions. Using advanced techniques, we show how temperature and nitrogen oxides affect the formation and behaviour of these particles. Our findings will improve our understanding on secondary organic particle and air quality models.
Laura Marie Dahler Heinlein, Junwei He, Michael Oluwatoyin Sunday, Fangzhou Guo, James Campbell, Allison Moon, Sukriti Kapur, Ting Fang, Kasey Edwards, Meeta Cesler-Maloney, Alyssa J. Burns, Jack Dibb, William Simpson, Manabu Shiraiwa, Becky Alexander, Jingqiu Mao, James H. Flynn III, Jochen Stutz, and Cort Anastasio
EGUsphere, https://doi.org/10.5194/egusphere-2025-824, https://doi.org/10.5194/egusphere-2025-824, 2025
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High-latitude cities like Fairbanks, Alaska, experience severe wintertime pollution episodes. While conventional wisdom holds that oxidation is slow under these conditions, field measurements find oxidized products in particles. To explore this, we measured oxidants in aqueous extracts of winter particles from Fairbanks. We find high concentrations of oxidants during illumination, indicating that particle photochemistry can be significant even in high latitudes during winter.
Rui Jin, Wei Hu, Peimin Duan, Ming Sheng, Dandan Liu, Ziye Huang, Mutong Niu, Libin Wu, Junjun Deng, and Pingqing Fu
Atmos. Chem. Phys., 25, 1805–1829, https://doi.org/10.5194/acp-25-1805-2025, https://doi.org/10.5194/acp-25-1805-2025, 2025
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The metabolic capacity of atmospheric microorganisms after settling into habitats is poorly understood. We studied the molecular composition of exometabolites for cultured typical airborne microbes and traced their metabolic processes. Bacteria and fungi produce highly oxidized exometabolites and have significant variations in metabolism among different strains. These insights are pivotal for assessing the biogeochemical impacts of atmospheric microorganisms following their deposition.
Sophie Bogler, Jun Zhang, Rico K. Y. Cheung, Kun Li, Andre S. H. Prevot, Imad El Haddad, and David M. Bell
EGUsphere, https://doi.org/10.5194/egusphere-2025-385, https://doi.org/10.5194/egusphere-2025-385, 2025
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Authentic aerosols emitted from residential wood stoves and open burning processes are only slightly oxidized by ozone in the atmosphere. Under dry conditions the reaction does not proceed to completion, while under high humidity conditions the reactivity proceeds further. These results indicate the reactivity with ozone is likely impacted by aerosol phase state (e.g. aerosol viscosity).
Michel Legrand, Mstislav Vorobyev, Daria Bokuchava, Stanislav Kutuzov, Andreas Plach, Andreas Stohl, Alexandra Khairedinova, Vladimir Mikhalenko, Maria Vinogradova, Sabine Eckhardt, and Susanne Preunkert
Atmos. Chem. Phys., 25, 1385–1399, https://doi.org/10.5194/acp-25-1385-2025, https://doi.org/10.5194/acp-25-1385-2025, 2025
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Past atmospheric NH3 pollution in south-eastern Europe was reconstructed by analysing ammonium in an ice core drilled at the Mount Elbrus (Caucasus, Russia). The observed 3.5-fold increase in ice concentrations between 1750 and 1990 CE is in good agreement with estimated past dominant ammonia emissions from agriculture, mainly from south European Russia and Türkiye. In contrast to present-day conditions, the ammonium level observed in 1750 CE indicates significant natural emissions at that time.
Mohammed Jaoui, Klara Nestorowicz, Krzysztof J. Rudzinski, Michael Lewandowski, Tadeusz E. Kleindienst, Julio Torres, Ewa Bulska, Witold Danikiewicz, and Rafal Szmigielski
Atmos. Chem. Phys., 25, 1401–1432, https://doi.org/10.5194/acp-25-1401-2025, https://doi.org/10.5194/acp-25-1401-2025, 2025
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Recent research has established the contribution of 1,3-butadiene (13BD) to organic aerosol formation with negative implications for urban air quality. Health effect studies have focused on whole particulate matter, but compounds responsible for adverse health effects remain uncertain. This study provides the effect of relative humidity and seed aerosol acidity on the chemical composition of aerosol formed from 13BD photooxidation.
Francesco Battaglia, Paola Formenti, Chiara Giorio, Mathieu Cazaunau, Edouard Pangui, Antonin Bergé, Aline Gratien, Thomas Bertin, Joël F. de Brito, Manolis N. Romanias, Vincent Michoud, Clarissa Baldo, Servanne Chevaillier, Gaël Noyalet, Philippe Decorse, Bénédicte Picquet-Varrault, and Jean-François Doussin
EGUsphere, https://doi.org/10.5194/egusphere-2024-4073, https://doi.org/10.5194/egusphere-2024-4073, 2025
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This paper presents an experimental investigation of the interactions between glyoxal, an important volatile organic compound, and mineral dust particles of size and composition typical of natural conditions. We show that their interactions modifies in a definitive way the concentrations of the gas phase and the properties of the dust, which could have important implications of the atmospheric composition and the Earth's climate.
Rongzhi Tang, Jialiang Ma, Ruifeng Zhang, Weizhen Cui, Yuanyuan Qin, Yangxi Chu, Yiming Qin, Alexander L. Vogel, and Chak K. Chan
Atmos. Chem. Phys., 25, 425–439, https://doi.org/10.5194/acp-25-425-2025, https://doi.org/10.5194/acp-25-425-2025, 2025
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This study provides laboratory evidence that the photosensitizers in biomass burning extracts can enhance sulfate formation in NaCl particles, primarily by triggering the formation of secondary oxidants under light and air conditions, with a lower contribution of direct photosensitization via triplets.
Anni Hartikainen, Mika Ihalainen, Deeksha Shukla, Marius Rohkamp, Arya Mukherjee, Quanfu He, Sandra Piel, Aki Virkkula, Delun Li, Tuukka Kokkola, Seongho Jeong, Hanna Koponen, Uwe Etzien, Anusmita Das, Krista Luoma, Lukas Schwalb, Thomas Gröger, Alexandre Barth, Martin Sklorz, Thorsten Streibel, Hendryk Czech, Benedikt Gündling, Markus Kalberer, Bert Buchholz, Andreas Hupfer, Thomas Adam, Thorsten Hohaus, Johan Øvrevik, Ralf Zimmermann, and Olli Sippula
EGUsphere, https://doi.org/10.5194/egusphere-2024-3836, https://doi.org/10.5194/egusphere-2024-3836, 2025
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Photochemical reactions altered the properties of kerosene-operated jet engine burner exhaust emissions, which were studied in laboratory using an oxidation flow reactor. Particle mass increased 300-fold as particles and gases became more oxidized. Light absorption increased, but the total direct radiative forcing efficiency was estimated to shift from positive to negative. The results highlight the importance of considering secondary aerosol formation when assessing the impacts of aviation.
Si Zhang, Yining Gao, Xinbei Xu, Luyao Chen, Can Wu, Zheng Li, Rongjie Li, Binyu Xiao, Xiaodi Liu, Rui Li, Fan Zhang, and Gehui Wang
Atmos. Chem. Phys., 24, 14177–14190, https://doi.org/10.5194/acp-24-14177-2024, https://doi.org/10.5194/acp-24-14177-2024, 2024
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Secondary organic aerosols (SOAs) from acetone photooxidation in the presence of various seeds were studied to illustrate SOA formation kinetics under ammonia-rich conditions. The oxidation mechanism of acetone was investigated using an observation-based model incorporating a Master Chemical Mechanism model. A higher SOA yield of acetone was observed compared to methylglyoxal due to an enhanced uptake of the small photooxidation products of acetone.
Adam Milsom, Adam M. Squires, Ben Laurence, Ben Wōden, Andrew J. Smith, Andrew D. Ward, and Christian Pfrang
Atmos. Chem. Phys., 24, 13571–13586, https://doi.org/10.5194/acp-24-13571-2024, https://doi.org/10.5194/acp-24-13571-2024, 2024
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We followed nano-structural changes in mixtures found in urban organic aerosol emissions (oleic acid, sodium oleate and fructose) during humidity change and ozone exposure. We demonstrate that self-assembly of fatty acid nanostructures can impact water uptake and chemical reactivity, affecting atmospheric lifetimes, urban air quality (preventing harmful emissions from degradation and enabling their long-range transport) and climate (affecting cloud formation), with implications for human health.
Kumiko Goto-Azuma, Remi Dallmayr, Yoshimi Ogawa-Tsukagawa, Nobuhiro Moteki, Tatsuhiro Mori, Sho Ohata, Yutaka Kondo, Makoto Koike, Motohiro Hirabayashi, Jun Ogata, Kyotaro Kitamura, Kenji Kawamura, Koji Fujita, Sumito Matoba, Naoko Nagatsuka, Akane Tsushima, Kaori Fukuda, and Teruo Aoki
Atmos. Chem. Phys., 24, 12985–13000, https://doi.org/10.5194/acp-24-12985-2024, https://doi.org/10.5194/acp-24-12985-2024, 2024
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We developed a continuous flow analysis system to analyze an ice core from northwestern Greenland and coupled it with an improved refractory black carbon (rBC) measurement technique. This allowed accurate high-resolution analyses of size distributions and concentrations of rBC particles with diameters of 70 nm–4 μm for the past 350 years. Our results provide crucial insights into rBC's climatic effects. We also found previous ice core studies substantially underestimated rBC mass concentrations.
Sergio Harb, Manuela Cirtog, Stéphanie Alage, Christopher Cantrell, Mathieu Cazaunau, Vincent Michoud, Edouard Pangui, Antonin Bergé, Chiara Giorio, Francesco Battaglia, and Bénédicte Picquet-Varrault
EGUsphere, https://doi.org/10.5194/egusphere-2024-3419, https://doi.org/10.5194/egusphere-2024-3419, 2024
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We investigated the reactions of α- and β-phellandrenes (from vegetation emissions) with NO3 radicals, a major nighttime oxidant from human activities. Using lab-based simulations, we examined these reactions and measured particle formation and by-products. Our findings reveal that α- and β-phellandrenes are efficient particle sources and enhance our understanding of biogenic-anthropogenic interactions and their contributions to atmospheric changes affecting climate and health.
Julia Pikmann, Frank Drewnick, Friederike Fachinger, and Stephan Borrmann
Atmos. Chem. Phys., 24, 12295–12321, https://doi.org/10.5194/acp-24-12295-2024, https://doi.org/10.5194/acp-24-12295-2024, 2024
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Cooking activities can contribute substantially to indoor and ambient aerosol. We performed a comprehensive study with laboratory measurements cooking 19 different dishes and ambient measurements at two Christmas markets measuring various particle properties and trace gases of emissions in real time. Similar emission characteristics were observed for dishes with the same preparation method, mainly due to similar cooking temperature and use of oil, with barbecuing as an especially strong source.
Han Zang, Zekun Luo, Chenxi Li, Ziyue Li, Dandan Huang, and Yue Zhao
Atmos. Chem. Phys., 24, 11701–11716, https://doi.org/10.5194/acp-24-11701-2024, https://doi.org/10.5194/acp-24-11701-2024, 2024
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Atmospheric organics are subject to synergistic oxidation by different oxidants, yet the mechanisms of such processes are poorly understood. Here, using direct measurements and kinetic modeling, we probe the nocturnal synergistic-oxidation mechanism of α-pinene by O3 and NO3 radicals and in particular the fate of peroxy radical intermediates of different origins, which will deepen our understanding of the monoterpene oxidation chemistry and its contribution to atmospheric particle formation.
Hui Yang, Fengfeng Dong, Li Xia, Qishen Huang, Shufeng Pang, and Yunhong Zhang
Atmos. Chem. Phys., 24, 11619–11635, https://doi.org/10.5194/acp-24-11619-2024, https://doi.org/10.5194/acp-24-11619-2024, 2024
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Atmospheric secondary aerosols, composed of organic and inorganic components, undergo complex reactions that impact their phase state. Using molecular spectroscopy, we showed that ammonium-promoted aqueous replacement reaction, unique to these aerosols, is closely linked to phase behavior. The interplay between reactions and aerosol phase state can cause atypical phase transition and irreversible changes in aerosol composition during hygroscopic cycles, further impacting atmospheric processes.
Xiaoli Shen, David M. Bell, Hugh Coe, Naruki Hiranuma, Fabian Mahrt, Nicholas A. Marsden, Claudia Mohr, Daniel M. Murphy, Harald Saathoff, Johannes Schneider, Jacqueline Wilson, Maria A. Zawadowicz, Alla Zelenyuk, Paul J. DeMott, Ottmar Möhler, and Daniel J. Cziczo
Atmos. Chem. Phys., 24, 10869–10891, https://doi.org/10.5194/acp-24-10869-2024, https://doi.org/10.5194/acp-24-10869-2024, 2024
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Single-particle mass spectrometry (SPMS) is commonly used to measure the chemical composition and mixing state of aerosol particles. Intercomparison of SPMS instruments was conducted. All instruments reported similar size ranges and common spectral features. The instrument-specific detection efficiency was found to be more dependent on particle size than type. All differentiated secondary organic aerosol, soot, and soil dust but had difficulties differentiating among minerals and dusts.
Adolfo González-Romero, Cristina González-Flórez, Agnesh Panta, Jesús Yus-Díez, Patricia Córdoba, Andres Alastuey, Natalia Moreno, Melani Hernández-Chiriboga, Konrad Kandler, Martina Klose, Roger N. Clark, Bethany L. Ehlmann, Rebecca N. Greenberger, Abigail M. Keebler, Phil Brodrick, Robert Green, Paul Ginoux, Xavier Querol, and Carlos Pérez García-Pando
Atmos. Chem. Phys., 24, 9155–9176, https://doi.org/10.5194/acp-24-9155-2024, https://doi.org/10.5194/acp-24-9155-2024, 2024
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In this research, we studied the dust-emitting properties of crusts and aeolian ripples from the Mojave Desert. These properties are key to understanding the effect of dust upon climate. We found two different playa lakes according to the groundwater regime, which implies differences in crusts' cohesion state and mineralogy, which can affect the dust emission potential and properties. We also compare them with Moroccan Sahara crusts and Icelandic top sediments.
Juanjuan Qin, Leiming Zhang, Yuanyuan Qin, Shaoxuan Shi, Jingnan Li, Zhao Shu, Yuwei Gao, Ting Qi, Jihua Tan, and Xinming Wang
Atmos. Chem. Phys., 24, 7575–7589, https://doi.org/10.5194/acp-24-7575-2024, https://doi.org/10.5194/acp-24-7575-2024, 2024
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The present research unveiled that acidity dominates while transition metal ions harmonize with the light absorption properties of humic-like substances (HULIS). Cu2+ has quenching effects on HULIS by complexation, hydrogen substitution, or electrostatic adsorption, with aromatic structures of HULIS. Such effects are less pronounced if from Mn2+, Ni2+, Zn2+, and Cu2+. Oxidized HULIS might contain electron-donating groups, whereas N-containing compounds might contain electron-withdrawing groups.
Adolfo González-Romero, Cristina González-Flórez, Agnesh Panta, Jesús Yus-Díez, Patricia Córdoba, Andres Alastuey, Natalia Moreno, Konrad Kandler, Martina Klose, Roger N. Clark, Bethany L. Ehlmann, Rebecca N. Greenberger, Abigail M. Keebler, Phil Brodrick, Robert O. Green, Xavier Querol, and Carlos Pérez García-Pando
Atmos. Chem. Phys., 24, 6883–6910, https://doi.org/10.5194/acp-24-6883-2024, https://doi.org/10.5194/acp-24-6883-2024, 2024
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The knowledge of properties from dust emitted in high latitudes such as in Iceland is scarce. This study focuses on the particle size, mineralogy, cohesion, and iron mode of occurrence and reflectance spectra of dust-emitting sediments. Icelandic top sediments have lower cohesion state, coarser particle size, distinctive mineralogy, and 3-fold bulk Fe content, with a large presence of magnetite compared to Saharan crusts.
Wangjin Yang, Jiawei Ma, Hongxing Yang, Fu Li, and Chong Han
Atmos. Chem. Phys., 24, 6757–6768, https://doi.org/10.5194/acp-24-6757-2024, https://doi.org/10.5194/acp-24-6757-2024, 2024
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We provide evidence that light enhances the conversion of SO2 to sulfates on non-photoactive mineral dust, where triplet states of SO2 (3SO2) can act as a pivotal trigger to generate sulfates. Photochemical sulfate formation depends on H2O, O2, and basicity of mineral dust. The SO2 photochemistry on non-photoactive mineral dust contributes to sulfates, highlighting previously unknown pathways to better explain the missing sources of atmospheric sulfates.
Lu Zhang, Jin Li, Yaojie Li, Xinlei Liu, Zhihan Luo, Guofeng Shen, and Shu Tao
Atmos. Chem. Phys., 24, 6323–6337, https://doi.org/10.5194/acp-24-6323-2024, https://doi.org/10.5194/acp-24-6323-2024, 2024
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Brown carbon (BrC) is related to radiative forcing and climate change. The BrC fraction from residential coal and biomass burning emissions, which were the major source of BrC, was characterized at the molecular level. The CHOS aromatic compounds explained higher light absorption efficiencies of biomass burning emissions compared to coal. The unique formulas of coal combustion aerosols were characterized by higher unsaturated compounds, and such information could be used for source appointment.
Wenli Liu, Longkun He, Yingjun Liu, Keren Liao, Qi Chen, and Mikinori Kuwata
Atmos. Chem. Phys., 24, 5625–5636, https://doi.org/10.5194/acp-24-5625-2024, https://doi.org/10.5194/acp-24-5625-2024, 2024
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Cooking is a major source of particles in urban areas. Previous studies demonstrated that the chemical lifetimes of cooking organic aerosols (COAs) were much shorter (~minutes) than the values reported by field observations (~hours). We conducted laboratory experiments to resolve the discrepancy by considering suppressed reactivity under low temperature. The parameterized k2–T relationships and observed surface temperature data were used to estimate the chemical lifetimes of COA particles.
Stephanie Arciva, Lan Ma, Camille Mavis, Chrystal Guzman, and Cort Anastasio
Atmos. Chem. Phys., 24, 4473–4485, https://doi.org/10.5194/acp-24-4473-2024, https://doi.org/10.5194/acp-24-4473-2024, 2024
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We measured changes in light absorption during the aqueous oxidation of six phenols with hydroxyl radical (●OH) or an organic triplet excited state (3C*). All the phenols formed light-absorbing secondary brown carbon (BrC), which then decayed with continued oxidation. Extrapolation to ambient conditions suggest ●OH is the dominant sink of secondary phenolic BrC in fog/cloud drops, while 3C* controls the lifetime of this light absorption in particle water.
Aaron Lieberman, Julietta Picco, Murat Onder, and Cort Anastasio
Atmos. Chem. Phys., 24, 4411–4419, https://doi.org/10.5194/acp-24-4411-2024, https://doi.org/10.5194/acp-24-4411-2024, 2024
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We developed a method that uses aqueous S(IV) to quantitatively convert NO2 to NO2−, which allows both species to be quantified using the Griess method. As an example of the utility of the method, we quantified both photolysis channels of nitrate, with and without a scavenger for hydroxyl radical (·OH). The results show that without a scavenger, ·OH reacts with nitrite to form nitrogen dioxide, suppressing the apparent quantum yield of NO2− and enhancing that of NO2.
Xingjun Fan, Ao Cheng, Xufang Yu, Tao Cao, Dan Chen, Wenchao Ji, Yongbing Cai, Fande Meng, Jianzhong Song, and Ping'an Peng
Atmos. Chem. Phys., 24, 3769–3783, https://doi.org/10.5194/acp-24-3769-2024, https://doi.org/10.5194/acp-24-3769-2024, 2024
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Molecular-level characteristics of high molecular weight (HMW) and low MW (LMW) humic-like substances (HULIS) were comprehensively investigated, where HMW HULIS had larger chromophores and larger molecular size than LMW HULIS and exhibited higher aromaticity and humification. Electrospray ionization high-resolution mass spectrometry revealed more aromatic molecules in HMW HULIS. HMW HULIS had more CHON compounds, while LMW HULIS had more CHO compounds.
Daniel A. Knopf, Markus Ammann, Thomas Berkemeier, Ulrich Pöschl, and Manabu Shiraiwa
Atmos. Chem. Phys., 24, 3445–3528, https://doi.org/10.5194/acp-24-3445-2024, https://doi.org/10.5194/acp-24-3445-2024, 2024
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The initial step of interfacial and multiphase chemical processes involves adsorption and desorption of gas species. This study demonstrates the role of desorption energy governing the residence time of the gas species at the environmental interface. A parameterization is formulated that enables the prediction of desorption energy based on the molecular weight, polarizability, and oxygen-to-carbon ratio of the desorbing chemical species. Its application to gas–particle interactions is discussed.
Feng Jiang, Kyla Siemens, Claudia Linke, Yanxia Li, Yiwei Gong, Thomas Leisner, Alexander Laskin, and Harald Saathoff
Atmos. Chem. Phys., 24, 2639–2649, https://doi.org/10.5194/acp-24-2639-2024, https://doi.org/10.5194/acp-24-2639-2024, 2024
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We investigated the optical properties, chemical composition, and formation mechanisms of secondary organic aerosol (SOA) and brown carbon (BrC) from the oxidation of indole with and without NO2 in the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) simulation chamber. This work is one of the very few to link the optical properties and chemical composition of indole SOA with and without NO2 by simulation chamber experiments.
Evangelia Kostenidou, Baptiste Marques, Brice Temime-Roussel, Yao Liu, Boris Vansevenant, Karine Sartelet, and Barbara D'Anna
Atmos. Chem. Phys., 24, 2705–2729, https://doi.org/10.5194/acp-24-2705-2024, https://doi.org/10.5194/acp-24-2705-2024, 2024
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Secondary organic aerosol (SOA) from gasoline vehicles can be a significant source of particulate matter in urban areas. Here the chemical composition of secondary volatile organic compounds and SOA produced by photo-oxidation of Euro 5 gasoline vehicle emissions was studied. The volatility of the SOA formed was calculated. Except for the temperature and the concentration of the aerosol, additional parameters may play a role in the gas-to-particle partitioning.
András Hoffer, Aida Meiramova, Ádám Tóth, Beatrix Jancsek-Turóczi, Gyula Kiss, Ágnes Rostási, Erika Andrea Levei, Luminita Marmureanu, Attila Machon, and András Gelencsér
Atmos. Chem. Phys., 24, 1659–1671, https://doi.org/10.5194/acp-24-1659-2024, https://doi.org/10.5194/acp-24-1659-2024, 2024
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Specific tracer compounds identified previously in controlled test burnings of different waste types in the laboratory were detected and quantified in ambient PM10 samples collected in five Hungarian and four Romanian settlements. Back-of-the-envelope calculations based on the relative emission factors of individual tracers suggested that the contribution of solid waste burning particulate emissions to ambient PM10 mass concentrations may be as high as a few percent.
Xiao-San Luo, Weijie Huang, Guofeng Shen, Yuting Pang, Mingwei Tang, Weijun Li, Zhen Zhao, Hanhan Li, Yaqian Wei, Longjiao Xie, and Tariq Mehmood
Atmos. Chem. Phys., 24, 1345–1360, https://doi.org/10.5194/acp-24-1345-2024, https://doi.org/10.5194/acp-24-1345-2024, 2024
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PM2.5 are air pollutants threatening health globally, but they are a mixture of chemical compositions from many sources and result in unequal toxicity. Which composition from which source of PM2.5 as the most hazardous object is a question hindering effective pollution control policy-making. With chemical and toxicity experiments, we found automobile exhaust and coal combustion to be priority emissions with higher toxic compositions for precise air pollution control, ensuring public health.
Matthew B. Goss and Jesse H. Kroll
Atmos. Chem. Phys., 24, 1299–1314, https://doi.org/10.5194/acp-24-1299-2024, https://doi.org/10.5194/acp-24-1299-2024, 2024
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The chemistry driving dimethyl sulfide (DMS) oxidation and subsequent sulfate particle formation in the atmosphere is poorly constrained. We oxidized two related compounds (dimethyl sulfoxide and dimethyl disulfide) in the laboratory under varied NOx conditions and measured the gas- and particle-phase products. These results demonstrate that both the OH addition and OH abstraction pathways for DMS oxidation contribute to particle formation via mechanisms that do not involve the SO2 intermediate.
Ryan J. Patnaude, Kathryn A. Moore, Russell J. Perkins, Thomas C. J. Hill, Paul J. DeMott, and Sonia M. Kreidenweis
Atmos. Chem. Phys., 24, 911–928, https://doi.org/10.5194/acp-24-911-2024, https://doi.org/10.5194/acp-24-911-2024, 2024
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In this study we examined the effect of atmospheric aging on sea spray aerosols (SSAs) to form ice and how newly formed secondary marine aerosols (SMAs) may freeze at cirrus temperatures (< −38 °C). Results show that SSAs freeze at different relative humidities (RHs) depending on the temperature and that the ice-nucleating ability of SSA was not hindered by atmospheric aging. SMAs are shown to freeze at high RHs and are likely inefficient at forming ice at cirrus temperatures.
Bartłomiej Witkowski, Priyanka Jain, Beata Wileńska, and Tomasz Gierczak
Atmos. Chem. Phys., 24, 663–688, https://doi.org/10.5194/acp-24-663-2024, https://doi.org/10.5194/acp-24-663-2024, 2024
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This article reports the results of the kinetic measurements for the aqueous oxidation of the 29 aliphatic alcohols by hydroxyl radical (OH) at different temperatures. The data acquired and the literature data were used to optimize a model for predicting the aqueous OH reactivity of alcohols and carboxylic acids and to estimate the atmospheric lifetimes of five terpenoic alcohols. The kinetic data provided new insights into the mechanism of aqueous oxidation of aliphatic molecules by the OH.
Junting Qiu, Xinlin Shen, Jiangyao Chen, Guiying Li, and Taicheng An
Atmos. Chem. Phys., 24, 155–166, https://doi.org/10.5194/acp-24-155-2024, https://doi.org/10.5194/acp-24-155-2024, 2024
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We studied reactions of secondary ozonides (SOZs) with amines. SOZs formed from ozonolysis of β-caryophyllene and α-humulene are found to be reactive to ethylamine and methylamine. Products from SOZs with various conformations reacting with the same amine had different functional groups. Our findings indicate that interaction of SOZs with amines in the atmosphere is very complicated, which is potentially a hitherto unrecognized source of N-containing compound formation.
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Short summary
This study provides new insight into the hydrolysis reaction mechanism, which was elucidated for atmospherically relevant organic nitrates using kinetic measurements, product identification, and theoretical calculations. The results help broaden our knowledge of the organic chemistry that impacts the fate of NOx, ozone production, aerosol phase processing, and aerosol composition.
This study provides new insight into the hydrolysis reaction mechanism, which was elucidated for...
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