Articles | Volume 17, issue 23
https://doi.org/10.5194/acp-17-14415-2017
© Author(s) 2017. 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-17-14415-2017
© Author(s) 2017. This work is distributed under
the Creative Commons Attribution 3.0 License.
the Creative Commons Attribution 3.0 License.
Research article
| 
05 Dec 2017
Research article |
| 05 Dec 2017
Compositional evolution of particle-phase reaction products and water in the heterogeneous OH oxidation of model aqueous organic aerosols
Man Mei Chim
Earth System Science Programme, Faculty of Science, The Chinese University of Hong Kong, Hong Kong, China
Chiu Tung Cheng
Earth System Science Programme, Faculty of Science, The Chinese University of Hong Kong, Hong Kong, China
present address: Atmosphere and Ocean Research Institute, The University of Tokyo, Tokyo, Japan
James F. Davies
Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California, USA
Thomas Berkemeier
School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, Atlanta, Georgia, USA
Manabu Shiraiwa
Department of Chemistry, School of Physical Sciences, University of California, Irvine, California, USA
Andreas Zuend
Department of Atmospheric and Oceanic Sciences, McGill University, Montreal, Québec, Canada
Man Nin Chan
CORRESPONDING AUTHOR
Earth System Science Programme, Faculty of Science, The Chinese University of Hong Kong, Hong Kong, China
The Institute of Environment, Energy and Sustainability, The Chinese University of Hong Kong, Hong Kong, China
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Jake Wilson, Ulrich Pöschl, Manabu Shiraiwa, and Thomas Berkemeier
Atmos. Chem. Phys., 21, 6175–6198, https://doi.org/10.5194/acp-21-6175-2021, https://doi.org/10.5194/acp-21-6175-2021, 2021
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Weigang Wang, Ting Lei, Andreas Zuend, Hang Su, Yafang Cheng, Yajun Shi, Maofa Ge, and Mingyuan Liu
Atmos. Chem. Phys., 21, 2179–2190, https://doi.org/10.5194/acp-21-2179-2021, https://doi.org/10.5194/acp-21-2179-2021, 2021
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Hoi Ki Lam, Rongshuang Xu, Jack Choczynski, James F. Davies, Dongwan Ham, Mijung Song, Andreas Zuend, Wentao Li, Ying-Lung Steve Tse, and Man Nin Chan
Atmos. Chem. Phys., 21, 2053–2066, https://doi.org/10.5194/acp-21-2053-2021, https://doi.org/10.5194/acp-21-2053-2021, 2021
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Manabu Shiraiwa and Ulrich Pöschl
Atmos. Chem. Phys., 21, 1565–1580, https://doi.org/10.5194/acp-21-1565-2021, https://doi.org/10.5194/acp-21-1565-2021, 2021
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Sabin Kasparoglu, Ying Li, Manabu Shiraiwa, and Markus D. Petters
Atmos. Chem. Phys., 21, 1127–1141, https://doi.org/10.5194/acp-21-1127-2021, https://doi.org/10.5194/acp-21-1127-2021, 2021
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Thomas Berkemeier, Masayuki Takeuchi, Gamze Eris, and Nga L. Ng
Atmos. Chem. Phys., 20, 15513–15535, https://doi.org/10.5194/acp-20-15513-2020, https://doi.org/10.5194/acp-20-15513-2020, 2020
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Ying Li, Douglas A. Day, Harald Stark, Jose L. Jimenez, and Manabu Shiraiwa
Atmos. Chem. Phys., 20, 8103–8122, https://doi.org/10.5194/acp-20-8103-2020, https://doi.org/10.5194/acp-20-8103-2020, 2020
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Havala O. T. Pye, Athanasios Nenes, Becky Alexander, Andrew P. Ault, Mary C. Barth, Simon L. Clegg, Jeffrey L. Collett Jr., Kathleen M. Fahey, Christopher J. Hennigan, Hartmut Herrmann, Maria Kanakidou, James T. Kelly, I-Ting Ku, V. Faye McNeill, Nicole Riemer, Thomas Schaefer, Guoliang Shi, Andreas Tilgner, John T. Walker, Tao Wang, Rodney Weber, Jia Xing, Rahul A. Zaveri, and Andreas Zuend
Atmos. Chem. Phys., 20, 4809–4888, https://doi.org/10.5194/acp-20-4809-2020, https://doi.org/10.5194/acp-20-4809-2020, 2020
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Acid rain is recognized for its impacts on human health and ecosystems, and programs to mitigate these effects have had implications for atmospheric acidity. Historical measurements indicate that cloud and fog droplet acidity has changed in recent decades in response to controls on emissions from human activity, while the limited trend data for suspended particles indicate acidity may be relatively constant. This review synthesizes knowledge on the acidity of atmospheric particles and clouds.
Rongshuang Xu, Hoi Ki Lam, Kevin R. Wilson, James F. Davies, Mijung Song, Wentao Li, Ying-Lung Steve Tse, and Man Nin Chan
Atmos. Chem. Phys., 20, 3879–3893, https://doi.org/10.5194/acp-20-3879-2020, https://doi.org/10.5194/acp-20-3879-2020, 2020
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Atmospheric particles, a complex mixture of inorganic salts, organic compounds and water, can continually undergo heterogeneous oxidation initiated by gas-phase oxidants at the particle surface. We found that ammonium sulfate can decelerate the rate of heterogeneous OH reaction with 2-methyltetrols when the inorganic-to-organic mass ratio increases. These results would suggest 2-methyltetrols are likely chemically stable against heterogeneous OH oxidation in the atmosphere.
Natalie R. Gervasi, David O. Topping, and Andreas Zuend
Atmos. Chem. Phys., 20, 2987–3008, https://doi.org/10.5194/acp-20-2987-2020, https://doi.org/10.5194/acp-20-2987-2020, 2020
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Organic aerosols have been shown to exist often in a semi-solid or amorphous, glassy state. Highly viscous particles behave differently than their well-mixed liquid analogues with consequences for a variety of aerosol processes. Here, we introduce a new predictive mixture viscosity model called AIOMFAC-VISC. It enables us to predict the viscosity of aqueous organic mixtures as a function of temperature and chemical composition, covering the full range of liquid, semi-solid, and glassy states.
Kyle Gorkowski, Thomas C. Preston, and Andreas Zuend
Atmos. Chem. Phys., 19, 13383–13407, https://doi.org/10.5194/acp-19-13383-2019, https://doi.org/10.5194/acp-19-13383-2019, 2019
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We present the new Binary Activity Thermodynamics (BAT) model, which is a water-sensitive reduced-complexity organic aerosol thermodynamics model. It can use bulk properties like O : C, molar mass, and RH to predict organic activity coefficients and water uptake behavior. We show applications in RH-dependent organic co-condensation, liquid–liquid phase separation, and Kohler curve predictions, and we validate the BAT model against laboratory measurements.
Mijung Song, Adrian M. Maclean, Yuanzhou Huang, Natalie R. Smith, Sandra L. Blair, Julia Laskin, Alexander Laskin, Wing-Sy Wong DeRieux, Ying Li, Manabu Shiraiwa, Sergey A. Nizkorodov, and Allan K. Bertram
Atmos. Chem. Phys., 19, 12515–12529, https://doi.org/10.5194/acp-19-12515-2019, https://doi.org/10.5194/acp-19-12515-2019, 2019
Erin Evoy, Adrian M. Maclean, Grazia Rovelli, Ying Li, Alexandra P. Tsimpidi, Vlassis A. Karydis, Saeid Kamal, Jos Lelieveld, Manabu Shiraiwa, Jonathan P. Reid, and Allan K. Bertram
Atmos. Chem. Phys., 19, 10073–10085, https://doi.org/10.5194/acp-19-10073-2019, https://doi.org/10.5194/acp-19-10073-2019, 2019
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We measured the diffusion rates of organic molecules in a number of proxies for secondary organic aerosol (SOA) and compared measured diffusion with predictions from two relations: the Stokes–Einstein relation and a fractional Stokes–Einstein relation. The fractional relation does a better job of predicting diffusion rates in this case. Output from an atmospheric model shows that mixing times predicted using the two relations differ by up to 1 order of magnitude at an altitude of ~ 3 km.
Hoi Ki Lam, Sze Man Shum, James F. Davies, Mijung Song, Andreas Zuend, and Man Nin Chan
Atmos. Chem. Phys., 19, 9581–9593, https://doi.org/10.5194/acp-19-9581-2019, https://doi.org/10.5194/acp-19-9581-2019, 2019
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We show the presence of dissolved inorganic salts could reduce the overall heterogeneous reactivity of organic compounds with gas–phase OH radicals at the surface by lowering the surface concentration of organic compounds. Until recently, the kinetic parameters reported in the literature were mostly measured based on experiments with pure organic particles. The lifetime of organic compounds or chemical tracers against heterogeneous OH reaction in the atmosphere could be longer than expected.
Olli-Pekka Tikkanen, Väinö Hämäläinen, Grazia Rovelli, Antti Lipponen, Manabu Shiraiwa, Jonathan P. Reid, Kari E. J. Lehtinen, and Taina Yli-Juuti
Atmos. Chem. Phys., 19, 9333–9350, https://doi.org/10.5194/acp-19-9333-2019, https://doi.org/10.5194/acp-19-9333-2019, 2019
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Ying Li and Manabu Shiraiwa
Atmos. Chem. Phys., 19, 5959–5971, https://doi.org/10.5194/acp-19-5959-2019, https://doi.org/10.5194/acp-19-5959-2019, 2019
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James F. Davies, Andreas Zuend, and Kevin R. Wilson
Atmos. Chem. Phys., 19, 2933–2946, https://doi.org/10.5194/acp-19-2933-2019, https://doi.org/10.5194/acp-19-2933-2019, 2019
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The formation of cloud droplets involves the condensation of water onto preexisting particles in the atmosphere. The efficiency of this process depends on the nature of the particles, and recent work has shown that organic-rich particles may exhibit a suppressed surface tension that promotes the formation of cloud droplets. In this technical note, we discuss the mechanism for this and highlight the evolution of surface tension as the key factor in the extent of surface effects.
Hoi Ki Lam, Kai Chung Kwong, Hon Yin Poon, James F. Davies, Zhenfa Zhang, Avram Gold, Jason D. Surratt, and Man Nin Chan
Atmos. Chem. Phys., 19, 2433–2440, https://doi.org/10.5194/acp-19-2433-2019, https://doi.org/10.5194/acp-19-2433-2019, 2019
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Organosulfates are ubiquitous in the atmosphere. We find that chemical transformation of IEPOX-derived organosulfates, one of the most abundant organosulfates, can generate inorganic sulfate through heterogeneous OH oxidation. The findings of this work provide new reaction pathways for recycling of inorganic and organic sulfur and may suggest that organosulfates could be reservoirs of inorganic sulfates in the atmosphere.
Wing-Sy Wong DeRieux, Ying Li, Peng Lin, Julia Laskin, Alexander Laskin, Allan K. Bertram, Sergey A. Nizkorodov, and Manabu Shiraiwa
Atmos. Chem. Phys., 18, 6331–6351, https://doi.org/10.5194/acp-18-6331-2018, https://doi.org/10.5194/acp-18-6331-2018, 2018
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The phase transition of organic particles between glassy and semi-solid states occurs at the glass transition temperature. We developed a method to predict glass transition temperatures and the viscosity of secondary organic aerosols using molecular composition, with consistent results with viscosity measurements. The viscosity of biomass burning particles was also estimated using the chemical composition measured by high-resolution mass spectrometry with two different ionization techniques.
Kai Chung Kwong, Man Mei Chim, James F. Davies, Kevin R. Wilson, and Man Nin Chan
Atmos. Chem. Phys., 18, 2809–2820, https://doi.org/10.5194/acp-18-2809-2018, https://doi.org/10.5194/acp-18-2809-2018, 2018
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To date, it remains unclear how organosulfates evolve over time in the atmosphere. We demonstrate that heterogeneous OH oxidation of sodium methyl sulfate, the smallest organosulfate found in atmospheric aerosols, is efficient. The oxidation can lead to the formation of sulfate radical anion and produce inorganic sulfate. In addition to OH radicals, sulfate radical anion chemistry can play a role in determining the evolution of sodium methyl sulfate and other organosulfates during oxidation.
Mallory L. Hinks, Julia Montoya-Aguilera, Lucas Ellison, Peng Lin, Alexander Laskin, Julia Laskin, Manabu Shiraiwa, Donald Dabdub, and Sergey A. Nizkorodov
Atmos. Chem. Phys., 18, 1643–1652, https://doi.org/10.5194/acp-18-1643-2018, https://doi.org/10.5194/acp-18-1643-2018, 2018
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We have observed a strong effect of relative humidity on the composition of particulate matter produced from the oxidation of toluene in clean air. At higher relative humidity, there was a significant reduction in the fraction of high-molecular-weight compounds present in the particles. The amount of particulate matter also decreased at higher relative humidity. The main implication of this study is that water vapor participates in the photooxidation of toluene in a complicated way.
Ting Lei, Andreas Zuend, Yafang Cheng, Hang Su, Weigang Wang, and Maofa Ge
Atmos. Chem. Phys., 18, 1045–1064, https://doi.org/10.5194/acp-18-1045-2018, https://doi.org/10.5194/acp-18-1045-2018, 2018
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Measurements and thermodynamic equilibrium predictions for organic–inorganic aerosols related to components from biomass burning emissions demonstrate a diversity of hygroscopic growth and shrinking behavior, which we observed using a hygroscopicity tandem differential mobility analyzer (HTDMA). Controlled laboratory experiments with single solutes and/or with mixed organic–inorganic systems of known phase state will be useful to constrain model parameters of thermodynamic equilibrium models.
Havala O. T. Pye, Andreas Zuend, Juliane L. Fry, Gabriel Isaacman-VanWertz, Shannon L. Capps, K. Wyat Appel, Hosein Foroutan, Lu Xu, Nga L. Ng, and Allen H. Goldstein
Atmos. Chem. Phys., 18, 357–370, https://doi.org/10.5194/acp-18-357-2018, https://doi.org/10.5194/acp-18-357-2018, 2018
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Thermodynamic modeling revealed that some but not all measurements of ammonium-to-sulfate ratios are consistent with theory. The measurement diversity likely explains the previously reported range of results regarding the suitability of thermodynamic modeling. Despite particles being predominantly phase separated, organic–inorganic interactions resulted in increased aerosol pH and partitioning towards the particle phase for highly oxygenated organic compounds compared to traditional methods.
Qing Mu, Gerhard Lammel, Christian N. Gencarelli, Ian M. Hedgecock, Ying Chen, Petra Přibylová, Monique Teich, Yuxuan Zhang, Guangjie Zheng, Dominik van Pinxteren, Qiang Zhang, Hartmut Herrmann, Manabu Shiraiwa, Peter Spichtinger, Hang Su, Ulrich Pöschl, and Yafang Cheng
Atmos. Chem. Phys., 17, 12253–12267, https://doi.org/10.5194/acp-17-12253-2017, https://doi.org/10.5194/acp-17-12253-2017, 2017
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Polycyclic aromatic hydrocarbons (PAHs) are hazardous pollutants with the largest emissions in East Asia. The regional WRF-Chem-PAH model has been developed to reflect the state-of-the-art understanding of current PAHs studies with several new or updated features. It is able to reasonably well simulate the concentration levels and particulate mass fractions of PAHs near the sources and at a remote outflow region of East Asia, in high spatial and temporal resolutions.
Thomas Berkemeier, Markus Ammann, Ulrich K. Krieger, Thomas Peter, Peter Spichtinger, Ulrich Pöschl, Manabu Shiraiwa, and Andrew J. Huisman
Atmos. Chem. Phys., 17, 8021–8029, https://doi.org/10.5194/acp-17-8021-2017, https://doi.org/10.5194/acp-17-8021-2017, 2017
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Kinetic process models are efficient tools used to unravel the mechanisms governing chemical and physical transformation in multiphase atmospheric chemistry. However, determination of kinetic parameters such as reaction rate or diffusion coefficients from multiple data sets is often difficult or ambiguous. This study presents a novel optimization algorithm and framework to determine these parameters in an automated fashion and to gain information about parameter uncertainty and uniqueness.
Andrea M. Arangio, Haijie Tong, Joanna Socorro, Ulrich Pöschl, and Manabu Shiraiwa
Atmos. Chem. Phys., 16, 13105–13119, https://doi.org/10.5194/acp-16-13105-2016, https://doi.org/10.5194/acp-16-13105-2016, 2016
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We have quantified environmentally persistent free radicals and reactive oxygen species (ROS) in size-segregated atmospheric aerosol particles. We suggest that ROS were formed by decomposition of secondary organic aerosols interacting with transition metal ions and quinones contained in humic-like substances. The results have significant implications for aqueous-phase and cloud processing of organic aerosols as well as adverse health effects upon respiratory deposition of aerosol particles.
Pascale S. J. Lakey, Thomas Berkemeier, Manuel Krapf, Josef Dommen, Sarah S. Steimer, Lisa K. Whalley, Trevor Ingham, Maria T. Baeza-Romero, Ulrich Pöschl, Manabu Shiraiwa, Markus Ammann, and Dwayne E. Heard
Atmos. Chem. Phys., 16, 13035–13047, https://doi.org/10.5194/acp-16-13035-2016, https://doi.org/10.5194/acp-16-13035-2016, 2016
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Chemical oxidation in the atmosphere removes pollutants and greenhouse gases but generates undesirable products such as secondary organic aerosol. Radicals are key intermediates in oxidation, but how they interact with aerosols is still not well understood. Here we use a laser to measure the loss of radicals onto oxidised aerosols generated in a smog chamber. The loss of radicals was controlled by the thickness or viscosity of the aerosols, confirmed by using sugar aerosols of known thickness.
Natasha Hodas, Andreas Zuend, Katherine Schilling, Thomas Berkemeier, Manabu Shiraiwa, Richard C. Flagan, and John H. Seinfeld
Atmos. Chem. Phys., 16, 12767–12792, https://doi.org/10.5194/acp-16-12767-2016, https://doi.org/10.5194/acp-16-12767-2016, 2016
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Discontinuities in apparent hygroscopicity below and above water saturation have been observed for organic and mixed organic-inorganic aerosol particles in both laboratory studies and in the ambient atmosphere. This work explores the extent to which such discontinuities are influenced by organic component molecular mass and viscosity, non-ideal thermodynamic interactions between aerosol components, and the combination of these factors.
Ying Li, Ulrich Pöschl, and Manabu Shiraiwa
Atmos. Chem. Phys., 16, 3327–3344, https://doi.org/10.5194/acp-16-3327-2016, https://doi.org/10.5194/acp-16-3327-2016, 2016
Haijie Tong, Andrea M. Arangio, Pascale S. J. Lakey, Thomas Berkemeier, Fobang Liu, Christopher J. Kampf, William H. Brune, Ulrich Pöschl, and Manabu Shiraiwa
Atmos. Chem. Phys., 16, 1761–1771, https://doi.org/10.5194/acp-16-1761-2016, https://doi.org/10.5194/acp-16-1761-2016, 2016
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We provide experimental evidence that terpene and isoprene SOA form substantial amounts of OH radicals upon interaction with liquid water and iron. Our measurements and model results imply that the chemical reactivity of SOA in the atmosphere, particularly in clouds, can be faster than previously thought. Inhalation and deposition of SOA particles in the human respiratory tract may lead to a substantial release of OH radicals in vivo, causing oxidative stress and adverse aerosol health effects.
G. Gržinić, T. Bartels-Rausch, T. Berkemeier, A. Türler, and M. Ammann
Atmos. Chem. Phys., 15, 13615–13625, https://doi.org/10.5194/acp-15-13615-2015, https://doi.org/10.5194/acp-15-13615-2015, 2015
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The heterogeneous loss of dinitrogen pentoxide (N2O5) to citric acid aerosol, a proxy for highly oxygenated secondary organic aerosol, is shown to be substantially lower than to other aqueous organic aerosol proxies investigated previously. This is attributed to the widely changing viscosity within the atmospherically relevant humidity range. It may explain some of the unexpectedly low loss rates of N2O5 to aerosol particles derived from field studies.
E. F. Mikhailov, G. N. Mironov, C. Pöhlker, X. Chi, M. L. Krüger, M. Shiraiwa, J.-D. Förster, U. Pöschl, S. S. Vlasenko, T. I. Ryshkevich, M. Weigand, A. L. D. Kilcoyne, and M. O. Andreae
Atmos. Chem. Phys., 15, 8847–8869, https://doi.org/10.5194/acp-15-8847-2015, https://doi.org/10.5194/acp-15-8847-2015, 2015
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Our manuscript describes the hygroscopic properties of accumulation- and coarse-mode aerosol particles sampled at the ZOTTO in central Siberia (61º N, 89º E). The hygroscopic growth measurements were supplemented with chemical analyses of the samples. In addition, the microstructure and chemical composition of aerosol particles were analyzed by x-ray micro-spectroscopy (STXM-NEXAFS) and transmission electron microscopy (TEM).
M. J. Tang, M. Shiraiwa, U. Pöschl, R. A. Cox, and M. Kalberer
Atmos. Chem. Phys., 15, 5585–5598, https://doi.org/10.5194/acp-15-5585-2015, https://doi.org/10.5194/acp-15-5585-2015, 2015
N. Hodas, A. Zuend, W. Mui, R. C. Flagan, and J. H. Seinfeld
Atmos. Chem. Phys., 15, 5027–5045, https://doi.org/10.5194/acp-15-5027-2015, https://doi.org/10.5194/acp-15-5027-2015, 2015
G. Ganbavale, A. Zuend, C. Marcolli, and T. Peter
Atmos. Chem. Phys., 15, 447–493, https://doi.org/10.5194/acp-15-447-2015, https://doi.org/10.5194/acp-15-447-2015, 2015
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This study presents a new, improved parameterisation of the temperature dependence of activity coefficients implemented in the AIOMFAC group-contribution model. The AIOMFAC model with the improved parameterisation is applicable for a large variety of aqueous organic as well as water-free organic solutions of relevance for atmospheric aerosols. The new model parameters were determined based on published and new thermodynamic equilibrium data covering a temperature range from ~190 to 440 K.
T. Berkemeier, M. Shiraiwa, U. Pöschl, and T. Koop
Atmos. Chem. Phys., 14, 12513–12531, https://doi.org/10.5194/acp-14-12513-2014, https://doi.org/10.5194/acp-14-12513-2014, 2014
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Glassy organic particles can serve as ice nuclei at low temperatures. We provide a rationale for these findings using a numerical aerosol diffusion model that describes particle phase state and its kinetics during simulated atmospheric updrafts dependent upon composition, size, updraft velocity, temperature and humidity. Our simulations suggest that aerosols from anthropogenic aromatic organics can be particularly relevant for ice cloud formation.
T. Lei, A. Zuend, W. G. Wang, Y. H. Zhang, and M. F. Ge
Atmos. Chem. Phys., 14, 11165–11183, https://doi.org/10.5194/acp-14-11165-2014, https://doi.org/10.5194/acp-14-11165-2014, 2014
G. Ganbavale, C. Marcolli, U. K. Krieger, A. Zuend, G. Stratmann, and T. Peter
Atmos. Chem. Phys., 14, 9993–10012, https://doi.org/10.5194/acp-14-9993-2014, https://doi.org/10.5194/acp-14-9993-2014, 2014
M. Shiraiwa, T. Berkemeier, K. A. Schilling-Fahnestock, J. H. Seinfeld, and U. Pöschl
Atmos. Chem. Phys., 14, 8323–8341, https://doi.org/10.5194/acp-14-8323-2014, https://doi.org/10.5194/acp-14-8323-2014, 2014
C. L. Loza, J. S. Craven, L. D. Yee, M. M. Coggon, R. H. Schwantes, M. Shiraiwa, X. Zhang, K. A. Schilling, N. L. Ng, M. R. Canagaratna, P. J. Ziemann, R. C. Flagan, and J. H. Seinfeld
Atmos. Chem. Phys., 14, 1423–1439, https://doi.org/10.5194/acp-14-1423-2014, https://doi.org/10.5194/acp-14-1423-2014, 2014
T. Berkemeier, A. J. Huisman, M. Ammann, M. Shiraiwa, T. Koop, and U. Pöschl
Atmos. Chem. Phys., 13, 6663–6686, https://doi.org/10.5194/acp-13-6663-2013, https://doi.org/10.5194/acp-13-6663-2013, 2013
A. J. Huisman, U. K. Krieger, A. Zuend, C. Marcolli, and T. Peter
Atmos. Chem. Phys., 13, 6647–6662, https://doi.org/10.5194/acp-13-6647-2013, https://doi.org/10.5194/acp-13-6647-2013, 2013
Related subject area
Subject: Aerosols | Research Activity: Laboratory Studies | Altitude Range: Troposphere | Science Focus: Chemistry (chemical composition and reactions)
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
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
Enhanced Sulfate Formation in Mixed Biomass Burning and Sea-salt Particles Mediated by Photosensitization: Effects of Chloride and Nitrogen-containing Compounds
Characterization of the particle size distribution, mineralogy, and Fe mode of occurrence of dust-emitting sediments from the Mojave Desert, California, USA
The lifetimes and potential change in planetary albedo owing to the oxidation of organic films extracted from atmospheric aerosol by hydroyxl (OH) radical oxidation at the air-water interface of aerosol particles
Atmospheric oxidation of 1,3-butadiene: influence of acidity and relative humidity on SOA composition and air toxic compounds
Measurement Report: Changes of ammonia emissions since the 18th century in south-eastern Europe inferred from an Elbrus (Caucasus, Russia) ice core record
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
Exometabolomic exploration of culturable airborne microorganisms from an urban atmosphere
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
Seasonal variations in photooxidant formation and light absorption in aqueous extracts of ambient particles
Variability in sediment particle size, mineralogy, and Fe mode of occurrence across dust-source inland drainage basins: the case of the lower Drâa Valley, Morocco
Gas–particle partitioning of toluene oxidation products: an experimental and modeling study
Chemically speciated air pollutant emissions from open burning of household solid waste from South Africa
Bulk and molecular-level composition of primary organic aerosol from wood, straw, cow dung, and plastic burning
Volatile oxidation products and secondary organosiloxane aerosol from D5 + OH at varying OH exposures
Molecular fingerprints and health risks of smoke from home-use incense burning
High enrichment of heavy metals in fine particulate matter through dust aerosol generation
Production of ice-nucleating particles (INPs) by fast-growing phytoplankton
Technical note: In situ measurements and modelling of the oxidation kinetics in films of a cooking aerosol proxy using a quartz crystal microbalance with dissipation monitoring (QCM-D)
Contrasting impacts of humidity on the ozonolysis of monoterpenes: insights into the multi-generation chemical mechanism
Quantifying the seasonal variations in and regional transport of PM2.5 in the Yangtze River Delta region, China: characteristics, sources, and health risks
Opinion: Atmospheric multiphase chemistry – past, present, and future
Distinct photochemistry in glycine particles mixed with different atmospheric nitrate salts
Effects of storage conditions on the molecular-level composition of organic aerosol particles
Characterization of gas and particle emissions from open burning of household solid waste from South Africa
Chemically distinct particle-phase emissions from highly controlled pyrolysis of three wood types
Predicting photooxidant concentrations in aerosol liquid water based on laboratory extracts of ambient particles
Physicochemical characterization of free troposphere and marine boundary layer ice-nucleating particles collected by aircraft in the eastern North Atlantic
Large differences of highly oxygenated organic molecules (HOMs) and low-volatile species in secondary organic aerosols (SOAs) formed from ozonolysis of β-pinene and limonene
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.
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.
Rongzhi Tang, Jialiang Ma, Ruifeng Zhang, Weizhen Cui, Yuanyuan Qin, Yangxi Chu, Yiming Qin, Alexander L. Vogel, and Chak K. Chan
EGUsphere, https://doi.org/10.5194/egusphere-2024-2633, https://doi.org/10.5194/egusphere-2024-2633, 2024
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This study provided laboratory evidence that the photosensitizers in biomass burning extracts can enhance the sulfate formation in NaCl particles, primarily by triggering the formation of secondary oxidants under light and air, with less contribution of direct photosensitization via triplets.
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.
Rosalie Shepherd, Martin King, Andrew Ward, Edward Stuckey, Rebecca Welbourn, Neil Brough, Adam Milsom, Christian Pfrang, and Thomas Arnold
EGUsphere, https://doi.org/10.5194/egusphere-2024-2367, https://doi.org/10.5194/egusphere-2024-2367, 2024
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Thin film formation at the air-water interface from material extracted from atmospheric aerosol was demonstrated, supporting core-shell morphology. The film thicknesses were approximately 10 Å and 17 Å for urban and remote extracts. Exposure to gas-phase OH radicals showed fast reactions and short lifetimes of around 1 hour. The effect on the Earth's radiative balance indicated that removing half of the film could significantly increase the top of the atmosphere albedo for urban films.
Mohammed Jaoui, Klara Nestorowicz, Krzysztof Rudzinski, Michael Lewandowski, Tadeusz Kleindienst, Julio Torres, Ewa Bulska, Witold Danikiewicz, and Rafal Szmigielski
EGUsphere, https://doi.org/10.5194/egusphere-2024-2032, https://doi.org/10.5194/egusphere-2024-2032, 2024
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Recent research has established the contribution of 1,3-butadiene (13BD) to organic aerosol formation with negative implications to urban air quality. Health effects 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 acidity on the chemical composition of aerosol formed from 13BD photooxidation.
Michel Legrand, Mstislav Vorobyev, Daria Bokuchava, Stanislav Kutuzov, Andreas Plach, Andreas Stohl, Alexandra Khairedinova, Vladimir Mikhalenko, Maria Vinogradova, Sabine Eckhardt, and Susanne Preunkert
EGUsphere, https://doi.org/10.5194/egusphere-2024-1381, https://doi.org/10.5194/egusphere-2024-1381, 2024
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A record of ammonium covering the years 1750 to 2008 was extracted from a 182-meter-long ice core drilled in 2009 at Mt. Elbrus in the Caucasus, Russia. Changes in ammonia emissions in southeastern Europe during the pre-industrial and industrial periods were investigated. The level of ammonium in 1750 indicates a significant contribution of natural sources to the ammonia budget, contrasting with present-day conditions, where agricultural emissions outweigh those from biogenic sources in Europe.
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.
Rui Jin, Wei Hu, Peimin Duan, Ming Sheng, Dandan Liu, Ziye Huang, Mutong Niu, Libin Wu, Junjun Deng, and Pingqing Fu
EGUsphere, https://doi.org/10.5194/egusphere-2024-1880, https://doi.org/10.5194/egusphere-2024-1880, 2024
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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 exometabolite and have significant variations in metabolism among different strains. These insights are pivotal for assessing the biogeochemical impacts of atmospheric microorganisms following their deposition.
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.
Lan Ma, Reed Worland, Laura Heinlein, Chrystal Guzman, Wenqing Jiang, Christopher Niedek, Keith J. Bein, Qi Zhang, and Cort Anastasio
Atmos. Chem. Phys., 24, 1–21, https://doi.org/10.5194/acp-24-1-2024, https://doi.org/10.5194/acp-24-1-2024, 2024
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We measured concentrations of three photooxidants – the hydroxyl radical, triplet excited states of organic carbon, and singlet molecular oxygen – in fine particles collected over a year. Concentrations are highest in extracts of fresh biomass burning particles, largely because they have the highest particle concentrations and highest light absorption. When normalized by light absorption, rates of formation for each oxidant are generally similar for the four particle types we observed.
Adolfo González-Romero, Cristina González-Flórez, Agnesh Panta, Jesús Yus-Díez, Cristina Reche, Patricia Córdoba, Natalia Moreno, Andres Alastuey, Konrad Kandler, Martina Klose, Clarissa Baldo, Roger N. Clark, Zongbo Shi, Xavier Querol, and Carlos Pérez García-Pando
Atmos. Chem. Phys., 23, 15815–15834, https://doi.org/10.5194/acp-23-15815-2023, https://doi.org/10.5194/acp-23-15815-2023, 2023
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The effect of dust emitted from desertic surfaces upon climate and ecosystems depends on size and mineralogy, but data from soil mineral atlases of desert soils are scarce. We performed particle-size distribution, mineralogy, and Fe speciation in southern Morocco. Results show coarser particles with high quartz proportion are near the elevated areas, while in depressed areas, sizes are finer, and proportions of clays and nano-Fe oxides are higher. This difference is important for dust modelling.
Victor Lannuque, Barbara D'Anna, Evangelia Kostenidou, Florian Couvidat, Alvaro Martinez-Valiente, Philipp Eichler, Armin Wisthaler, Markus Müller, Brice Temime-Roussel, Richard Valorso, and Karine Sartelet
Atmos. Chem. Phys., 23, 15537–15560, https://doi.org/10.5194/acp-23-15537-2023, https://doi.org/10.5194/acp-23-15537-2023, 2023
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Large uncertainties remain in understanding secondary organic aerosol (SOA) formation from toluene oxidation. In this study, speciation measurements in gaseous and particulate phases were carried out, providing partitioning and volatility data on individual toluene SOA components at different temperatures. A new detailed oxidation mechanism was developed to improve modeled speciation, and effects of different processes involved in gas–particle partitioning at the molecular scale are explored.
Xiaoliang Wang, Hatef Firouzkouhi, Judith C. Chow, John G. Watson, Steven Sai Hang Ho, Warren Carter, and Alexandra S. M. De Vos
Atmos. Chem. Phys., 23, 15375–15393, https://doi.org/10.5194/acp-23-15375-2023, https://doi.org/10.5194/acp-23-15375-2023, 2023
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Open burning of municipal solid waste emits chemicals that are harmful to the environment. This paper reports source profiles and emission factors for PM2.5 species and acidic/alkali gases from laboratory combustion of 10 waste categories (including plastics and biomass) that represent open burning in South Africa. Results will be useful for health and climate impact assessments, speciated emission inventories, source-oriented dispersion models, and receptor-based source apportionment.
Jun Zhang, Kun Li, Tiantian Wang, Erlend Gammelsæter, Rico K. Y. Cheung, Mihnea Surdu, Sophie Bogler, Deepika Bhattu, Dongyu S. Wang, Tianqu Cui, Lu Qi, Houssni Lamkaddam, Imad El Haddad, Jay G. Slowik, Andre S. H. Prevot, and David M. Bell
Atmos. Chem. Phys., 23, 14561–14576, https://doi.org/10.5194/acp-23-14561-2023, https://doi.org/10.5194/acp-23-14561-2023, 2023
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We conducted burning experiments to simulate various types of solid fuel combustion, including residential burning, wildfires, agricultural burning, cow dung, and plastic bag burning. The chemical composition of the particles was characterized using mass spectrometers, and new potential markers for different fuels were identified using statistical analysis. This work improves our understanding of emissions from solid fuel burning and offers support for refined source apportionment.
Hyun Gu Kang, Yanfang Chen, Yoojin Park, Thomas Berkemeier, and Hwajin Kim
Atmos. Chem. Phys., 23, 14307–14323, https://doi.org/10.5194/acp-23-14307-2023, https://doi.org/10.5194/acp-23-14307-2023, 2023
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D5 is an emerging anthropogenic pollutant that is ubiquitous in indoor and urban environments, and the OH oxidation of D5 forms secondary organosiloxane aerosol (SOSiA). Application of a kinetic box model that uses a volatility basis set (VBS) showed that consideration of oxidative aging (aging-VBS) predicts SOSiA formation much better than using a standard-VBS model. Ageing-dependent parameterization is needed to accurately model SOSiA to assess the implications of siloxanes for air quality.
Kai Song, Rongzhi Tang, Jingshun Zhang, Zichao Wan, Yuan Zhang, Kun Hu, Yuanzheng Gong, Daqi Lv, Sihua Lu, Yu Tan, Ruifeng Zhang, Ang Li, Shuyuan Yan, Shichao Yan, Baoming Fan, Wenfei Zhu, Chak K. Chan, Maosheng Yao, and Song Guo
Atmos. Chem. Phys., 23, 13585–13595, https://doi.org/10.5194/acp-23-13585-2023, https://doi.org/10.5194/acp-23-13585-2023, 2023
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Incense burning is common in Asia, posing threats to human health and air quality. However, less is known about its emissions and health risks. Full-volatility organic species from incense-burning smoke are detected and quantified. Intermediate-volatility volatile organic compounds (IVOCs) are crucial organics accounting for 19.2 % of the total emission factors (EFs) and 40.0 % of the secondary organic aerosol (SOA) estimation, highlighting the importance of incorporating IVOCs into SOA models.
Qianqian Gao, Shengqiang Zhu, Kaili Zhou, Jinghao Zhai, Shaodong Chen, Qihuang Wang, Shurong Wang, Jin Han, Xiaohui Lu, Hong Chen, Liwu Zhang, Lin Wang, Zimeng Wang, Xin Yang, Qi Ying, Hongliang Zhang, Jianmin Chen, and Xiaofei Wang
Atmos. Chem. Phys., 23, 13049–13060, https://doi.org/10.5194/acp-23-13049-2023, https://doi.org/10.5194/acp-23-13049-2023, 2023
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Dust is a major source of atmospheric aerosols. Its chemical composition is often assumed to be similar to the parent soil. However, this assumption has not been rigorously verified. Dust aerosols are mainly generated by wind erosion, which may have some chemical selectivity. Mn, Cd and Pb were found to be highly enriched in fine-dust (PM2.5) aerosols. In addition, estimation of heavy metal emissions from dust generation by air quality models may have errors without using proper dust profiles.
Daniel C. O. Thornton, Sarah D. Brooks, Elise K. Wilbourn, Jessica Mirrielees, Alyssa N. Alsante, Gerardo Gold-Bouchot, Andrew Whitesell, and Kiana McFadden
Atmos. Chem. Phys., 23, 12707–12729, https://doi.org/10.5194/acp-23-12707-2023, https://doi.org/10.5194/acp-23-12707-2023, 2023
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A major uncertainty in our understanding of clouds and climate is the sources and properties of the aerosol on which clouds grow. We found that aerosol containing organic matter from fast-growing marine phytoplankton was a source of ice-nucleating particles (INPs). INPs facilitate freezing of ice crystals at warmer temperatures than otherwise possible and therefore change cloud formation and properties. Our results show that ecosystem processes and the properties of sea spray aerosol are linked.
Adam Milsom, Shaojun Qi, Ashmi Mishra, Thomas Berkemeier, Zhenyu Zhang, and Christian Pfrang
Atmos. Chem. Phys., 23, 10835–10843, https://doi.org/10.5194/acp-23-10835-2023, https://doi.org/10.5194/acp-23-10835-2023, 2023
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Aerosols and films are found indoors and outdoors. Our study measures and models reactions of a cooking aerosol proxy with the atmospheric oxidant ozone relying on a low-cost but sensitive technique based on mass changes and film rigidity. We found that film morphology changed and film rigidity increased with evidence of surface crust formation during ozone exposure. Our modelling results demonstrate clear potential to take this robust method to the field for reaction monitoring.
Shan Zhang, Lin Du, Zhaomin Yang, Narcisse Tsona Tchinda, Jianlong Li, and Kun Li
Atmos. Chem. Phys., 23, 10809–10822, https://doi.org/10.5194/acp-23-10809-2023, https://doi.org/10.5194/acp-23-10809-2023, 2023
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In this study, we have investigated the distinct impacts of humidity on the ozonolysis of two structurally different monoterpenes (limonene and Δ3-carene). We found that the molecular structure of precursors can largely influence the SOA formation under high RH by impacting the multi-generation reactions. Our results could advance knowledge on the roles of water content in aerosol formation and inform ongoing research on particle environmental effects and applications in models.
Yangzhihao Zhan, Min Xie, Wei Zhao, Tijian Wang, Da Gao, Pulong Chen, Jun Tian, Kuanguang Zhu, Shu Li, Bingliang Zhuang, Mengmeng Li, Yi Luo, and Runqi Zhao
Atmos. Chem. Phys., 23, 9837–9852, https://doi.org/10.5194/acp-23-9837-2023, https://doi.org/10.5194/acp-23-9837-2023, 2023
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Although the main source contribution of pollution is secondary inorganic aerosols in Nanjing, health risks mainly come from industry sources and vehicle emissions. Therefore, the development of megacities should pay more attention to the health burden of vehicle emissions, coal combustion, and industrial processes. This study provides new insight into assessing the relationship between source apportionment and health risks and can provide valuable insight into air pollution strategies.
Jonathan P. D. Abbatt and A. R. Ravishankara
Atmos. Chem. Phys., 23, 9765–9785, https://doi.org/10.5194/acp-23-9765-2023, https://doi.org/10.5194/acp-23-9765-2023, 2023
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With important climate and air quality impacts, atmospheric multiphase chemistry involves gas interactions with aerosol particles and cloud droplets. We summarize the status of the field and discuss potential directions for future growth. We highlight the importance of a molecular-level understanding of the chemistry, along with atmospheric field studies and modeling, and emphasize the necessity for atmospheric multiphase chemists to interact widely with scientists from neighboring disciplines.
Zhancong Liang, Zhihao Cheng, Ruifeng Zhang, Yiming Qin, and Chak K. Chan
Atmos. Chem. Phys., 23, 9585–9595, https://doi.org/10.5194/acp-23-9585-2023, https://doi.org/10.5194/acp-23-9585-2023, 2023
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In this study, we found that the photolysis of sodium nitrate leads to a much quicker decay of free amino acids (FAAs, with glycine as an example) in the particle phase than ammonium nitrate photolysis, which is likely due to the molecular interactions between FAAs and different nitrate salts. Since sodium nitrate likely co-exists with FAAs in the coarse-mode particles, particulate nitrate photolysis can possibly contribute to a rapid decay of FAAs and affect atmospheric nitrogen cycling.
Julian Resch, Kate Wolfer, Alexandre Barth, and Markus Kalberer
Atmos. Chem. Phys., 23, 9161–9171, https://doi.org/10.5194/acp-23-9161-2023, https://doi.org/10.5194/acp-23-9161-2023, 2023
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Detailed chemical analysis of organic aerosols is necessary to better understand their effects on climate and health. Aerosol samples are often stored for days to months before analysis. We examined the effects of storage conditions (i.e., time, temperature, and aerosol storage on filters or as solvent extracts) on composition and found significant changes in the concentration of individual compounds, indicating that sample storage can strongly affect the detailed chemical particle composition.
Xiaoliang Wang, Hatef Firouzkouhi, Judith C. Chow, John G. Watson, Warren Carter, and Alexandra S. M. De Vos
Atmos. Chem. Phys., 23, 8921–8937, https://doi.org/10.5194/acp-23-8921-2023, https://doi.org/10.5194/acp-23-8921-2023, 2023
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Open burning of household and municipal solid waste is a common practice in developing countries and is a significant source of air pollution. However, few studies have measured emissions from open burning of waste. This study determined gas and particulate emissions from open burning of 10 types of household solid-waste materials. These results can improve emission inventories, air quality management, and assessment of the health and climate effects of open burning of household waste.
Anita M. Avery, Mariam Fawaz, Leah R. Williams, Tami Bond, and Timothy B. Onasch
Atmos. Chem. Phys., 23, 8837–8854, https://doi.org/10.5194/acp-23-8837-2023, https://doi.org/10.5194/acp-23-8837-2023, 2023
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Pyrolysis is the thermal decomposition of fuels like wood which occurs during combustion or as an isolated process. During combustion, some pyrolysis products are emitted directly, while others are oxidized in the combustion process. This work describes the chemical composition of particle-phase pyrolysis products in order to investigate both the uncombusted emissions from wildfires and the fuel that participates in combustion.
Lan Ma, Reed Worland, Wenqing Jiang, Christopher Niedek, Chrystal Guzman, Keith J. Bein, Qi Zhang, and Cort Anastasio
Atmos. Chem. Phys., 23, 8805–8821, https://doi.org/10.5194/acp-23-8805-2023, https://doi.org/10.5194/acp-23-8805-2023, 2023
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Although photooxidants are important in airborne particles, little is known of their concentrations. By measuring oxidants in a series of particle dilutions, we predict their concentrations in aerosol liquid water (ALW). We find •OH concentrations in ALW are on the order of 10−15 M, similar to their cloud/fog values, while oxidizing triplet excited states and singlet molecular oxygen have ALW values of ca. 10−13 M and 10−12 M, respectively, roughly 10–100 times higher than in cloud/fog drops.
Daniel A. Knopf, Peiwen Wang, Benny Wong, Jay M. Tomlin, Daniel P. Veghte, Nurun N. Lata, Swarup China, Alexander Laskin, Ryan C. Moffet, Josephine Y. Aller, Matthew A. Marcus, and Jian Wang
Atmos. Chem. Phys., 23, 8659–8681, https://doi.org/10.5194/acp-23-8659-2023, https://doi.org/10.5194/acp-23-8659-2023, 2023
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Ambient particle populations and associated ice-nucleating particles (INPs)
were examined from particle samples collected on board aircraft in the marine
boundary layer and free troposphere in the eastern North Atlantic during
summer and winter. Chemical imaging shows distinct differences in the
particle populations seasonally and with sampling altitudes, which are
reflected in the INP types. Freezing parameterizations are derived for
implementation in cloud-resolving and climate models.
Dandan Liu, Yun Zhang, Shujun Zhong, Shuang Chen, Qiaorong Xie, Donghuan Zhang, Qiang Zhang, Wei Hu, Junjun Deng, Libin Wu, Chao Ma, Haijie Tong, and Pingqing Fu
Atmos. Chem. Phys., 23, 8383–8402, https://doi.org/10.5194/acp-23-8383-2023, https://doi.org/10.5194/acp-23-8383-2023, 2023
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Based on ultra-high-resolution mass spectrometry analysis, we found that β-pinene oxidation-derived highly oxygenated organic molecules (HOMs) exhibit higher yield at high ozone concentration, while limonene oxidation-derived HOMs exhibit higher yield at moderate ozone concentration. The distinct molecular response of HOMs and low-volatile species in different biogenic secondary organic aerosols to ozone concentrations provides a new clue for more accurate air quality prediction and management.
Cited articles
Al-Kindi, S. S., Pope, F. D., Beddows, D. C., Bloss, W. J., and Harrison, R. M.: Size-dependent chemical ageing of oleic acid aerosol under dry and humidified conditions, Atmos. Chem. Phys., 16, 15561–15579, https://doi.org/10.5194/acp-16-15561-2016, 2016.
Arangio, A. M., Slade, J. H., Berkemeier, T., Pöschl, U., Knopf, D. A., and Shiraiwa, M.: Multiphase chemical kinetics of OH radical uptake by molecular organic markers of biomass burning aerosols: humidity and temperature dependence, surface reaction, and bulk diffusion, J. Phys. Chem. A, 119, 4533–4544, 2015.
Bennett, J. E. and Summers, R.: Product studies of the mutual termination reactions of sec-alkylperoxy radicals: evidence for non-cyclic termination, Can. J. Chem., 52, 1377–1379, 1974.
Berkemeier, T., Huisman, A. J., Ammann, M., Shiraiwa, M., Koop, T., and Pöschl, U.: Kinetic regimes and limiting cases of gas uptake and heterogeneous reactions in atmospheric aerosols and clouds: a general classification scheme, Atmos. Chem. Phys., 13, 6663–6686, https://doi.org/10.5194/acp-13-6663-2013, 2013.
Berkemeier, T., Steimer, S. S., Krieger, U. K., Peter, T., Pöschl, U., Ammann, M., and Shiraiwa, M.: Ozone uptake on glassy, semi-solid and liquid organic matter and the role of reactive oxygen intermediates in atmospheric aerosol chemistry, Phys. Chem. Chem. Phys., 18, 12662–12674, 2016.
Booth, A. M., Montague, W. J., Barley, M. H., Topping, D. O., McFiggans, G., Garforth, A., and Percival, C. J.: Solid state and sub-cooled liquid vapour pressures of cyclic aliphatic dicarboxylic acids, Atmos. Chem. Phys., 11, 655–665, https://doi.org/10.5194/acp-11-655-2011, 2011.
Braban, C. F., Carroll, M. F., Styler, S. A., and Abbatt, J. P.: Phase transitions of malonic and oxalic acid aerosols, J. Phys. Chem. A, 107, 6594–6602, 2003.
Broekhuizen, K. E., Thornberry, T., Kumar, P. P., and Abbatt, J. P. D.: Formation of cloud condensation nuclei by oxidative processing: unsaturated fatty acids, J. Geophys. Res.-Atmos., 109, D24, https://doi.org/10.1029/2004JD005298, 2004.
Brooks, B., Smith, M., Hill, M., and O'Dowd, C.: Size-differentiated volatility analysis of internally mixed laboratory-generated aerosol, J. Aerosol Sci., 33, 555–579, 2002.
Brüggemann, M., Karu, E., Stelzer, T., and Hoffmann, T.: Real-time analysis of ambient organic aerosols using aerosol flowing atmospheric-pressure afterglow mass spectrometry (AeroFAPA-MS), Environ. Sci. Technol., 49, 5571–5578, 2015.
Cappa, C. D. and Wilson, K. R.: Multi-generation gas-phase oxidation, equilibrium partitioning, and the formation and evolution of secondary organic aerosol, Atmos. Chem. Phys., 12, 9505–9528, https://doi.org/10.5194/acp-12-9505-2012, 2012.
Cappa, C. D., Che, D. L., Kessler, S. H., Kroll, J. H., and Wilson, K. R.: Variations in organic aerosol optical and hygroscopic properties upon heterogeneous OH oxidation, J. Geophys. Res.-Atmos., 116, D15, https://doi.org/10.1029/2011JD015918, 2011.
Chan, M. N., Choi, M. Y., Ng, N. L., and Chan, C. K.: Hygroscopicity of water-soluble organic compounds in atmospheric aerosols: amino acids and biomass burning derived organic species, Environ. Sci. Technol., 39, 1555–1562, 2005.
Chan, M. N., Kreidenweis, S. M., and Chan, C. K.: Measurements of the hygroscopic and deliquescence properties of organic compounds of different solubilities in water and their relationship with cloud condensation nuclei activities, Environ. Sci. Technol., 42, 3602–3608, 2008.
Chan, M. N., Nah, T., and Wilson, K. R.: Real time in situ chemical characterization of sub-micron organic aerosols using direct analysis in real time mass spectrometry (DART-MS): the effect of aerosol size and volatility, Analyst, 138, 3749–3757, 2013.
Chan, M. N., Zhang, H., Goldstein, A. H., and Wilson, K. R.: Role of water and phase in the heterogeneous oxidation of solid and aqueous succinic acid aerosol by hydroxyl radicals, J. Phys. Chem. C, 118, 28978–28992, 2014.
Chen, C., Stewart, D. J., Reid, J. P., Zhang, Y. H., Ohm, P., Dutcher, C. S., and Clegg, S. L.: Organic component vapor pressures and hygroscopicities of aqueous aerosol measured by optical tweezers, J. Phys. Chem. A, 119, 704–718, 2015.
Cheng, C. T., Chan, M. N., and Wilson, K. R.: The role of alkoxy radicals in the heterogeneous reaction of two structural isomers of dimethylsuccinic acid, Phys. Chem. Chem. Phys., 17, 25309–25321, 2015.
Cheng, C. T., Chan, M. N., and Wilson, K. R.: Importance of unimolecular HO2 elimination in the heterogeneous OH reaction of highly oxygenated tartaric acid aerosol, J. Phys. Chem. A, 120, 5887–5896, 2016.
Chim, M. M., Chow, C. Y., Davies, J. F., and Chan, M. N.: Effects of relative humidity and particle phase water on the heterogeneous OH oxidation of 2-methylglutaric acid aqueous droplets, J. Phys. Chem. A, https://doi.org/10.1021/acs.jpca.6b11606, 2017.
Clegg, S. L., Seinfeld, J. H., and Brimblecombe, P.: Thermodynamic modelling of aqueous aerosols containing electrolytes and dissolved organic compounds, J. Aerosol Sci., 32, 713–738, 2001.
Cody, R. B.: Observation of molecular ions and analysis of nonpolar compounds with the direct analysis in real time ion source, Anal. Chem., 81, 1101–1107, 2008.
Cody, R. B., Laramée, J. A., and Durst, H. D.: Versatile new ion source for the analysis of materials in open air under ambient conditions, Anal. Chem., 77, 2297–2302, 2005.
Compernolle, S., Ceulemans, K., and Müller, J.-F.: EVAPORATION: a new vapour pressure estimation methodfor organic molecules including non-additivity and intramolecular interactions, Atmos. Chem. Phys., 11, 9431–9450, https://doi.org/10.5194/acp-11-9431-2011, 2011.
Davies, J. F. and Wilson, K. R.: Nanoscale interfacial gradients formed by the reactive uptake of OH radicals onto viscous aerosol surfaces, Chem. Sci., 6, 7020–7027, 2015.
Davies, J. F. and Wilson, K. R.: Raman spectroscopy of isotopic water diffusion in ultraviscous, glassy, and gel states in aerosol by use of optical tweezers, Anal. Chem., 88, 2361–2366, 2016.
Dennis-Smither, B. J., Miles, R. E., and Reid, J. P.: Oxidative aging of mixed oleic acid/sodium chloride aerosol particles, J. Geophys. Res.-Atmos., 117, D20204, https://doi.org/10.1029/2012JD018163, 2012.
Doezema, L. A., Longin, T., Cody, W., Perraud, V., Dawson, M. L., Ezell, M. J., Greaves, J., Johnson, K. R., and Finlayson-Pitts, B. J.: Analysis of secondary organic aerosols in air using extractive electrospray ionization mass spectrometry (EESI-MS), RSC Adv., 2, 2930–2938, 2012.
Donahue, N., Robinson, A., Stanier, C., and Pandis, S.: Coupled partitioning, dilution, and chemical aging of semivolatile organics, Environ. Sci. Technol., 40, 2635–2643, 2006.
Doussin, J.-F. and Monod, A.: Structure–activity relationship for the estimation of OH-oxidation rate constants of carbonyl compounds in the aqueous phase, Atmos. Chem. Phys., 13, 11625–11641, https://doi.org/10.5194/acp-13-11625-2013, 2013.
Gallimore, P. J., Achakulwisut, P., Pope, F. D., Davies, J. F., Spring, D. R., and Kalberer, M.: Importance of relative humidity in the oxidative ageing of organic aerosols: case study of the ozonolysis of maleic acid aerosol, Atmos. Chem. Phys., 11, 12181–12195, https://doi.org/10.5194/acp-11-12181-2011, 2011.
Gallimore, P. J. and Kalberer, M.: Characterizing an extractive electrospray ionization (EESI) source for the online mass spectrometry analysis of organic aerosols, Environ. Sci. Technol., 47, 7324–7331, 2013.
Ganbavale, G., Marcolli, C., Krieger, U. K., Zuend, A., Stratmann, G., and Peter, T.: Experimental determination of the temperature dependence of water activities for a selection of aqueous organic solutions, Atmos. Chem. Phys., 14, 9993–10012, https://doi.org/10.5194/acp-14-9993-2014, 2014.
George, I., Chang, R.-W., Danov, V., Vlasenko, A., and Abbatt, J.: Modification of cloud condensation nucleus activity of organic aerosols by hydroxyl radical heterogeneous oxidation, Atmos. Environ., 43, 5038–5045, 2009.
George, I. J. and Abbatt, J. P. D.: Heterogeneous oxidation of atmospheric aerosol particles by gas-phase radicals, Nat. Chem., 2, 713–722, 2010.
Harmon, C. W., Ruehl, C. R., Cappa, C. D., and Wilson, K. R.: A statistical description of the evolution of cloud condensation nuclei activity during the heterogeneous oxidation of squalane and bis(2-ethylhexyl) sebacate aerosol by hydroxyl radicals, Phys. Chem. Chem. Phys., 15, 9679–9693, 2013.
Houle, F. A., Hinsberg, W. D., and Wilson, K. R.: Oxidation of a model alkane aerosol by OH radical: the emergent nature of reactive uptake, Phys. Chem. Chem. Phys., 17, 4412–4423, 2015.
Jimenez, J., Canagaratna, M., Donahue, N., Prevot, A., Zhang, Q., Kroll, J. H., DeCarlo, P. F., Allan, J. D., Coe, H., Ng, N., and Aiken, A. C.: Evolution of organic aerosols in the atmosphere, Science, 326, 1525–1529, 2009.
Jing, B., Tong, S., Liu, Q., Li, K., Wang, W., Zhang, Y., and Ge, M.: Hygroscopic behavior of multicomponent organic aerosols and their internal mixtures with ammonium sulfate, Atmos. Chem. Phys., 16, 4101–4118, https://doi.org/10.5194/acp-16-4101-2016, 2016.
Kroll, J. H., Donahue, N. M., Jimenez, J. L., Kessler, S. H., Canagaratna, M. R., Wilson, K. R., Altieri, K. E., Mazzoleni, L. R., Wozniak, A. S., and Bluhm, H.: Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol, Nat. Chem., 3, 133–139, 2011.
Kroll, J. H., Lim, C. Y., Kessler, S. H., and Wilson, K. R.: Heterogeneous oxidation of atmospheric organic aerosol: kinetics of changes to the amount and oxidation state of particle-phase organic carbon, J. Phys. Chem. A, 119, 10767–10783, 2015.
Kundu, S., Kawamura, K., Kobayashi, M., Tachibana, E., Lee, M., Fu, P. Q., and Jung, J.: A sub-decadal trend in diacids in atmospheric aerosols in eastern Asia, Atmos. Chem. Phys., 16, 585–596, https://doi.org/10.5194/acp-16-585-2016, 2016.
Kwok, E. S. and Atkinson, R.: Estimation of hydroxyl radical reaction rate constants for gas-phase organic compounds using a structure-reactivity relationship: an update, Atmos. Environ., 29, 1685–1695, 1995.
Lambe, A. T., Onasch, T. B., Massoli, P., Croasdale, D. R., Wright, J. P., Ahern, A. T., Williams, L. R., Worsnop, D. R., Brune, W. H., and Davidovits, P.: Laboratory studies of the chemical composition and cloud condensation nuclei (CCN) activity of secondary organic aerosol (SOA) and oxidized primary organic aerosol (OPOA), Atmos. Chem. Phys., 11, 8913–8928, https://doi.org/10.5194/acp-11-8913-2011, 2011.
Li, X. D., Yang, Z., Fu, P., Yu, J., Lang, Y. C., Liu, D., Ono, K., and Kawamura, K.: High abundances of dicarboxylic acids, oxocarboxylic acids, and α-dicarbonyls in fine aerosols (PM2.5) in Chengdu, China during wintertime haze pollution, Environ. Sci. Pollut. R., 22, 12902–12918, 2015.
Ma, Q., Ma, J., Liu, C., Lai, C., and He, H.: Laboratory study on the hygroscopic behavior of external and internal C2–C4 dicarboxylic acid–NaCl mixtures, Environ. Sci. Technol., 47, 10381–10388, 2013.
Marcolli, C., Luo, B., and Peter, T.: Mixing of the organic aerosol fractions: liquids as the thermodynamically stable phases, J. Phys. Chem. A, 108, 2216–2224, 2004.
Marsh, A., Miles, R. E. H., Rovelli, G., Cowling, A. G., Nandy, L., Dutcher, C. S., and Reid, J. P.: Influence of organic compound functionality on aerosol hygroscopicity: dicarboxylic acids, alkyl-substituents, sugars and amino acids, Atmos. Chem. Phys., 17, 5583–5599, https://doi.org/10.5194/acp-17-5583-2017, 2017.
Mikhailov, E., Vlasenko, S., Martin, S. T., Koop, T., and Pöschl, U.: Amorphous and crystalline aerosol particles interacting with water vapor: conceptual framework and experimental evidence for restructuring, phase transitions and kinetic limitations, Atmos. Chem. Phys., 9, 9491–9522, https://doi.org/10.5194/acp-9-9491-2009, 2009.
Mochida, M. and Kawamura, K.: Hygroscopic properties of levoglucosan and related organic compounds characteristic to biomass burning aerosol particles, J. Geophys. Res.-Atmos., 109, D21, https://doi.org/10.1029/2004JD004962, 2004.
Monod, A. and Doussin, J.: Structure-activity relationship for the estimation of OH-oxidation rate constants of aliphatic organic compounds in the aqueous phase: alkanes, alcohols, organic acids and bases, Atmos. Environ., 42, 7611–7622, 2008.
Nah, T., Chan, M., Leone, S. R., and Wilson, K. R.: Real time in situ chemical characterization of submicrometer organic particles using direct analysis in real time-mass spectrometry, Anal. Chem., 85, 2087–2095, 2013.
Pankow, J. F.: An absorption model of the gas/aerosol partitioning involved in the formation of secondary organic aerosol, Atmos. Environ., 28, 189–193, 1994.
Pankow, J. F. and Asher, W. E.: SIMPOL.1: a simple group contribution method for predicting vapor pressures and enthalpies of vaporization of multifunctional organic compounds, Atmos. Chem. Phys., 8, 2773–2796, https://doi.org/10.5194/acp-8-2773-2008, 2008.
Parsons, M. T., Mak, J., Lipetz, S. R., and Bertram, A. K.: Deliquescence of malonic, succinic, glutaric, and adipic acid particles, J. Geophys. Res.-Atmos., 109, D6, https://doi.org/10.1029/2003JD004075, 2004.
Peeters, J., Fantechi, G., and Vereecken, L.: A generalized structure-activity relationship for the decomposition of (substituted) alkoxy radicals, J. Atmos. Chem., 48, 59–80, 2004.
Peng, C., Chan, M. N., and Chan, C. K.: The hygroscopic properties of dicarboxylic and multifunctional acids: measurements and UNIFAC predictions, Environ. Sci. Technol., 35, 4495–4501, 2001.
Preston, T. C. and Reid, J. P.: Accurate and efficient determination of the radius, refractive index, and dispersion of weakly absorbing spherical particle using whispering gallery modes, J. Opt. Soc. Am. B, 30, 2113–2122, 2013.
Rickards, A. M., Miles, R. E., Davies, J. F., Marshall, F. H., and Reid, J. P.: Measurements of the sensitivity of aerosol hygroscopicity and the κ parameter to the O∕C ratio, J. Phys. Chem. A, 117, 14120–14131, 2013.
Rudich, Y., Donahue, N. M., and Mentel, T. F.: Aging of organic aerosol: bridging the gap between laboratory and field studies, Annu. Rev. Phys. Chem., 58, 321–352, 2007.
Russell, G. A.: Deuterium-isotope effects in the autoxidation of aralkyl hydrocarbons. Mechanism of the interaction of peroxy radicals, J. Am. Chem. Soc., 79, 3871–3877, 1957.
Shilling, J. E., King, S. M., Mochida, M., Worsnop, D. R., and Martin, S. T.: Mass spectral evidence that small changes in composition caused by oxidative aging processes alter aerosol CCN properties, J. Phys. Chem. A, 111, 3358–3368, 2007.
Shiraiwa, M., Ammann, M., Koop, T., and Pöschl, U.: Gas uptake and chemical aging of semisolid organic aerosol particles, P. Natl. Acad. Sci. USA, 108, 11003–11008, 2011.
Slade, J. H. and Knopf, D. A.: Multiphase OH oxidation kinetics of organic aerosol: the role of particle phase state and relative humidity, Geophys. Res. Lett., 41, 5297–5306, 2014.
Slade, J. H., Shiraiwa, M., Arangio, A., Su, H., Pöschl, U., Wang, J., and Knopf, D. A.: Cloud droplet activation through oxidation of organic aerosol influenced by temperature and particle phase state, Geophys. Res. Lett., 44, 1583–1591, 2017.
Smith, J. D., Kroll, J. H., Cappa, C. D., Che, D. L., Liu, C. L., Ahmed, M., Leone, S. R., Worsnop, D. R., and Wilson, K. R.: The heterogeneous reaction of hydroxyl radicals with sub-micron squalane particles: a model system for understanding the oxidative aging of ambient aerosols, Atmos. Chem. Phys., 9, 3209–3222, https://doi.org/10.5194/acp-9-3209-2009, 2009.
Topping, D., Barley, M., Bane, M. K., Higham, N., Aumont, B., Dingle, N., and McFiggans, G.: UManSysProp v1.0: an online and open-source facility for molecular property prediction and atmospheric aerosol calculations, Geosci. Model Dev., 9, 899–914, https://doi.org/10.5194/gmd-9-899-2016, 2016.
Vereecken, L. and Peeters, J.: Decomposition of substituted alkoxy radicals – Part I: a generalized structure–activity relationship for reaction barrier heights, Phys. Chem. Chem. Phys., 11, 9062–9074, 2009.
Wexler, A. S. and Clegg, S. L.: Atmospheric aerosol models for systems including the ions H+, NH4+, Na+, SO42−, NO3−, Cl−, Br−, and H2O, J. Geophys. Res.-Atmos., 107, D14, https://doi.org/10.1029/2001JD000451, 2002.
Wiegel, A. A., Wilson, K. R., Hinsberg, W. D., and Houle, F. A.: Stochastic methods for aerosol chemistry: a compact molecular description of functionalization and fragmentation in the heterogeneous oxidation of squalane aerosol by OH radicals, Phys. Chem. Chem. Phys., 17, 4398–4411, 2015.
Wiegel, A. A., Liu, M. J., Hinsberg, W. D., Wilson, K. R., and Houle, F. A.: Diffusive confinement of free radical intermediates in the OH radical oxidation of semisolid aerosols, Phys. Chem. Chem. Phys., 19, 6814–6830, 2017.
Wong, J. P. S., Lee, A. K. Y., Slowik, J. G., Cziczo, D. J., Leaitch, W. R., Macdonald, A., and Abbatt, J. P. D.: Oxidation of ambient biogenic secondary organic aerosol by hydroxyl radicals: effects on cloud condensation nuclei activity, Geophys. Res. Lett., 38, L22805, https://doi.org/10.1029/2011GL049351, 2011.
Zhao, Y., Fairhurst, M. C., Wingen, L. M., Perraud, V., Ezell, M. J., and Finlayson-Pitts, B. J.: New insights into atmospherically relevant reaction systems using direct analysis in real-time mass spectrometry (DART-MS), Atmos. Meas. Tech., 10, 1373–1386, https://doi.org/10.5194/amt-10-1373-2017, 2017.
Zuend, A., Marcolli, C., Luo, B. P., and Peter, T.: A thermodynamic model of mixed organic-inorganic aerosols to predict activity coefficients, Atmos. Chem. Phys., 8, 4559–4593, https://doi.org/10.5194/acp-8-4559-2008, 2008.
Zuend, A., Marcolli, C., Peter, T., and Seinfeld, J. H.: Computation of liquid-liquid equilibria and phase stabilities: implications for RH-dependent gas/particle partitioning of organic-inorganic aerosols, Atmos. Chem. Phys., 10, 7795–7820, https://doi.org/10.5194/acp-10-7795-2010, 2010.
Zuend, A., Marcolli, C., Booth, A. M., Lienhard, D. M., Soonsin, V., Krieger, U. K., Topping, D. O., McFiggans, G., Peter, T., and Seinfeld, J. H.: New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups, Atmos. Chem. Phys., 11, 9155–9206, https://doi.org/10.5194/acp-11-9155-2011, 2011.
Zuend, A. and Seinfeld, J. H.: Modeling the gas-particle partitioning of secondary organic aerosol: the importance of liquid-liquid phase separation, Atmos. Chem. Phys., 12, 3857–3882, https://doi.org/10.5194/acp-12-3857-2012, 2012.
Short summary
In this work, we report that methyl-substituted succinic acid present at or near the surface of aqueous organic droplets can be efficiently oxidized by gas-phase OH radicals. The alkoxy radical chemistry appears to be an important reaction pathway. In addition, our model simulations reveal the relative importance of functionalization and fragmentation processes, alongside volatilization, in the evolution of the particle-phase reaction, which is largely dependent on the extent of oxidation.
In this work, we report that methyl-substituted succinic acid present at or near the surface of...
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