Articles | Volume 24, issue 1
https://doi.org/10.5194/acp-24-663-2024
© Author(s) 2024. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-24-663-2024
© Author(s) 2024. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
17 Jan 2024
Research article |
| 17 Jan 2024
| 17 Jan 2024
Temperature-dependent aqueous OH kinetics of C2–C10 linear and terpenoid alcohols and diols: new rate coefficients, structure–activity relationship, and atmospheric lifetimes
Bartłomiej Witkowski
CORRESPONDING AUTHOR
University of Warsaw, Faculty of Chemistry, al. Żwirki i Wigury 101, 02-089 Warsaw, Poland
Priyanka Jain
University of Warsaw, Faculty of Chemistry, al. Żwirki i Wigury 101, 02-089 Warsaw, Poland
Beata Wileńska
University of Warsaw, Faculty of Chemistry, al. Żwirki i Wigury 101, 02-089 Warsaw, Poland
Tomasz Gierczak
University of Warsaw, Faculty of Chemistry, al. Żwirki i Wigury 101, 02-089 Warsaw, Poland
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This article provides new insights into the molecular composition of fine, light-absorbing organic aerosols emitted by biomass burning. Laboratory-generated aerosol was extracted into water and analyzed with liquid chromatography-mass spectrometry, identifying over 350 new water-soluble wood burning tracers. This study also examines the toxicities and atmospheric lifetimes, revealing that the newly identified molecules are harmful and can undergo chemical processing in atmospheric hydrometeors.
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This article describes a comprehensive investigation of the aqueous oxidation of 4-nitrophenol (4NP) by hydroxyl radicals (OH). The reaction was carried out in a laboratory photoreactor. We report the formation of key intermediates under different pH conditions and the evolution of the light absorption of the reaction solution. The results provide new insights into the formation and removal (chemical bleaching) of light-absorbing organic aerosols (atmospheric brown carbon).
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This article provides new insights into the molecular composition of fine, light-absorbing organic aerosols emitted by biomass burning. Laboratory-generated aerosol was extracted into water and analyzed with liquid chromatography-mass spectrometry, identifying over 350 new water-soluble wood burning tracers. This study also examines the toxicities and atmospheric lifetimes, revealing that the newly identified molecules are harmful and can undergo chemical processing in atmospheric hydrometeors.
Bartłomiej Witkowski, Priyanka Jain, and Tomasz Gierczak
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This article describes a comprehensive investigation of the aqueous oxidation of 4-nitrophenol (4NP) by hydroxyl radicals (OH). The reaction was carried out in a laboratory photoreactor. We report the formation of key intermediates under different pH conditions and the evolution of the light absorption of the reaction solution. The results provide new insights into the formation and removal (chemical bleaching) of light-absorbing organic aerosols (atmospheric brown carbon).
Chelsea E. Stockwell, Agnieszka Kupc, Bartłomiej Witkowski, Ranajit K. Talukdar, Yong Liu, Vanessa Selimovic, Kyle J. Zarzana, Kanako Sekimoto, Carsten Warneke, Rebecca A. Washenfelder, Robert J. Yokelson, Ann M. Middlebrook, and James M. Roberts
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This work investigates the total conversion of particle-bound nitrogen and organic carbon across platinum and molybdenum catalysts followed by NO–O3 chemiluminescence and nondispersive infrared CO2 detection. We show the instrument is an accurate particle mass measurement method and demonstrate its ability to calibrate particle mass measurement instrumentation through comparisons with a calibrated particle-into-liquid sampler coupled to an electrospray ionization source of a mass spectrometer.
Related subject area
Subject: Aerosols | Research Activity: Laboratory Studies | Altitude Range: Troposphere | Science Focus: Chemistry (chemical composition and reactions)
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
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
Boosting aerosol surface effects: strongly enhanced cooperative surface propensity of atmospherically relevant organic molecular ions in aqueous solution
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
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
Enhanced sulfate formation in mixed biomass burning and sea-salt interactions mediated by photosensitization: effects of chloride, nitrogen-containing compounds, and atmospheric aging
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
The role of surface-active macromolecules in the ice nucleating ability of lignin, Snomax, and agricultural soil extracts
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
Copper accelerates photochemically induced radical chemistry of iron-containing SOA
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
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
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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
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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.
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.
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.
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.
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.
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.
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.
Kathleen A. Thompson, Paul Bieber, Anna J. Miller, Nicole Link, Benjamin J. Murray, and Nadine Borduas-Dedekind
EGUsphere, https://doi.org/10.5194/egusphere-2024-2827, https://doi.org/10.5194/egusphere-2024-2827, 2024
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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. Hydrophobic interfaces play an important role in the ice-nucleating activity of organic matter; as the complexity of the sample increases, the hydrophobic interfaces in the bulk compete with the air-water interface.
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.
Kevin Kilchhofer, Markus Ammann, Laura Torrent, Ka Yuen Cheung, and Peter Aaron Alpert
EGUsphere, https://doi.org/10.5194/egusphere-2024-3226, https://doi.org/10.5194/egusphere-2024-3226, 2024
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Aerosol particles composed of metal complexes generate radicals as the result of photochemical reactions. 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 a decreased photochemical activity and use a copper-induced reoxidation reaction.
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.
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.
Cited articles
Adams, G. E., Boag, J. W., and Michael, B. D.: Reactions of the hydroxyl radical, Part 2 – Determination of absolute rate constants, T. Faraday Soc., 61, 1417–1424, https://doi.org/10.1039/TF9656101417, 1965.
Aljawhary, D., Zhao, R., Lee, A. K. Y., Wang, C., and Abbatt, J. P. D.: Kinetics, Mechanism, and Secondary Organic Aerosol Yield of Aqueous Phase Photo-oxidation of α-Pinene Oxidation Products, J. Phys. Chem. A, 120, 1395–1407, https://doi.org/10.1021/acs.jpca.5b06237, 2016.
Amorim, J. V., Wu, S., Klimchuk, K., Lau, C., Williams, F. J., Huang, Y., and Zhao, R.: pH Dependence of the OH Reactivity of Organic Acids in the Aqueous Phase, Environ. Sci. Technol., 54, 12484–12492, https://doi.org/10.1021/acs.est.0c03331, 2020.
Amorim, J. V., Guo, X., Gautam, T., Fang, R., Fotang, C., Williams, F. J., and Zhao, R.: Photo-oxidation of pinic acid in the aqueous phase: a mechanistic investigation under acidic and basic pH conditions, Environ. Sci.-Atmos., 1, 276–287, https://doi.org/10.1039/D1EA00031D, 2021.
Anbar, M., Meyerstein, D., and Neta, P.: Reactivity of aliphatic compounds towards hydroxyl radicals, J. Chem. Soc. B., 742–747, https://doi.org/10.1039/J29660000742, 1966.
Atkinson, R.: Estimations of OH radical rate constants from H-atom abstraction from CH and OH bonds over the temperature range 250–1000 K, Int. J. Chem. Kinet., 18, 555–568, https://doi.org/10.1002/kin.550180506, 1986a.
Atkinson, R.: Kinetics and mechanisms of the gas-phase reactions of the hydroxyl radical with organic compounds under atmospheric conditions, Chem. Rev., 86, 69–201, https://doi.org/10.1021/cr00071a004, 1986b.
Atkinson, R.: A structure-activity relationship for the estimation of rate constants for the gas-phase reactions of OH radicals with organic compounds, Int. J. Chem. Kinet., 19, 799–828, https://doi.org/10.1002/kin.550190903, 1987.
Belsito, D., Bickers, D., Bruze, M., Calow, P., Greim, H., Hanifin, J. M., Rogers, A. E., Saurat, J. H., Sipes, I. G., and Tagami, H.: A toxicologic and dermatologic assessment of cyclic and non-cyclic terpene alcohols when used as fragrance ingredients, Food Chem. Toxicol., 46, S1–S71, https://doi.org/10.1016/j.fct.2008.06.085, 2008.
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, https://doi.org/10.1139/v74-209, 1974.
Bräuer, P., Mouchel-Vallon, C., Tilgner, A., Mutzel, A., Böge, O., Rodigast, M., Poulain, L., van Pinxteren, D., Wolke, R., Aumont, B., and Herrmann, H.: Development of a protocol for the auto-generation of explicit aqueous-phase oxidation schemes of organic compounds, Atmos. Chem. Phys., 19, 9209–9239, https://doi.org/10.5194/acp-19-9209-2019, 2019.
Buxton, G. V., Greenstock, C. L., Helman, W. P., and Ross, A. B.: Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (
Carlton, A. G., Christiansen, A. E., Flesch, M. M., Hennigan, C. J., and Sareen, N.: Multiphase Atmospheric Chemistry in Liquid Water: Impacts and Controllability of Organic Aerosol, Acc. Chem. Res., 53, 1715–1723, https://doi.org/10.1021/acs.accounts.0c00301, 2020.
Ceacero-Vega, A. A., Ballesteros, B., Bejan, I., Barnes, I., Jiménez, E., and Albaladejo, J.: Kinetics and Mechanisms of the Tropospheric Reactions of Menthol, Borneol, Fenchol, Camphor, and Fenchone with Hydroxyl Radicals (OH) and Chlorine Atoms (Cl), J. Phys. Chem. A, 116, 4097–4107, https://doi.org/10.1021/jp212076g, 2012.
Chandler, D.: Interfaces and the driving force of hydrophobic assembly, Nature, 437, 640–647, https://doi.org/10.1038/nature04162, 2005.
Chen, H., Su, X., He, J., Zhang, P., Xu, H., and Zhou, C.: Investigation on combustion characteristics of cyclopentanol/diesel fuel blends in an optical engine, Renew. Energ., 167, 811–829, https://doi.org/10.1016/j.renene.2020.11.155, 2021.
Cheng, Y., Zheng, G., Wei, C., Mu, Q., Zheng, B., Wang, Z., Gao, M., Zhang, Q., He, K., Carmichael, G., Pöschl, U., and Su, H.: Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China, Sci. Adv., 2, 1–11, https://doi.org/10.1126/sciadv.1601530, 2016.
Chin, M. and Wine, P. H.: A Temperature-Dependent Competitive Kinetics Study of the Aqueous-Phase Reactions of OH Radicals with Formate, Formic Acid, Acetate, Acetic Acid, and Hydrated Formaldehyde, Symposium on Aquatic and Surface Photochemistry, at the 203rd National Meeting of the American-Chemical-Society, San Francisco, Ca, April 5–10, WOS:A1994, 85–96, eBook ISBN 9781351069847, https://doi.org/10.1201/9781351069847, 1994.
Claeys, M., Iinuma, Y., Szmigielski, R., Surratt, J. D., Blockhuys, F., Van Alsenoy, C., Bołge, O., Sierau, B., Goìmez-Gonzaìlez, Y., Vermeylen, R., Van der Veken, P., Shahgholi, M., Chan, A. W. H., Herrmann, H., Seinfeld, J. H., and Maenhaut, W.: Terpenylic Acid and Related Compounds from the Oxidation of α-Pinene: Implications for New Particle Formation and Growth above Forests, Environ. Sci. Technol., 43, 6976–6982, https://doi.org/10.1021/es9007596, 2009.
Das, P., Das, P. K., and Arunan, E.: Conformational Stability and Intramolecular Hydrogen Bonding in 1,2-Ethanediol and 1,4-Butanediol, J. Phys. Chem. A, 119, 3710–3720, https://doi.org/10.1021/jp512686s, 2015.
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.
Enami, S. and Sakamoto, Y.: OH-Radical Oxidation of Surface-Active cis-Pinonic Acid at the Air–Water Interface, J. Phys. Chem. A, 120, 3578–3587, https://doi.org/10.1021/acs.jpca.6b01261, 2016.
Ervens, B.: Modeling the Processing of Aerosol and Trace Gases in Clouds and Fogs, Chem. Rev., 115, 4157–4198, https://doi.org/10.1021/cr5005887, 2015.
Ervens, B., Gligorovski, S., and Herrmann, H.: Temperature-dependent rate constants for hydroxyl radical reactions with organic compounds in aqueous solutions, Phys. Chem. Chem. Phys., 5, 1811–1824, https://doi.org/10.1039/B300072A, 2003.
Ervens, B., Sorooshian, A., Aldhaif, A. M., Shingler, T., Crosbie, E., Ziemba, L., Campuzano-Jost, P., Jimenez, J. L., and Wisthaler, A.: Is there an aerosol signature of chemical cloud processing?, Atmos. Chem. Phys., 18, 16099–16119, https://doi.org/10.5194/acp-18-16099-2018, 2018.
Fichan, I., Larroche, C., and Gros, J. B.: Water Solubility, Vapor Pressure, and Activity Coefficients of Terpenes and Terpenoids, J. Chem. Eng. Data., 44, 56–62, https://doi.org/10.1021/je980070+, 1999.
Fu, P. Q., Kawamura, K., Chen, J., Charrière, B., and Sempéré, R.: Organic molecular composition of marine aerosols over the Arctic Ocean in summer: contributions of primary emission and secondary aerosol formation, Biogeosciences, 10, 653–667, https://doi.org/10.5194/bg-10-653-2013, 2013.
Fuzzi, S., Baltensperger, U., Carslaw, K., Decesari, S., Denier van der Gon, H., Facchini, M. C., Fowler, D., Koren, I., Langford, B., Lohmann, U., Nemitz, E., Pandis, S., Riipinen, I., Rudich, Y., Schaap, M., Slowik, J. G., Spracklen, D. V., Vignati, E., Wild, M., Williams, M., and Gilardoni, S.: Particulate matter, air quality and climate: lessons learned and future needs, Atmos. Chem. Phys., 15, 8217–8299, https://doi.org/10.5194/acp-15-8217-2015, 2015.
Gligorovski, S., Rousse, D., George, C., and Herrmann, H.: Rate constants for the OH reactions with oxygenated organic compounds in aqueous solution, Int. J. Chem. Kinet., 41, 309–326, https://doi.org/10.1002/kin.20405, 2009.
Goldstein, A. H. and Galbally, I. E.: Known and unexplored organic constituents in the earth's atmosphere, Environ. Sci. Technol., 41, 1514–1521, https://doi.org/10.1021/es072476p, 2007.
González-Sánchez, J. M., Brun, N., Wu, J., Morin, J., Temime-Roussel, B., Ravier, S., Mouchel-Vallon, C., Clément, J. L., and Monod, A.: On the importance of atmospheric loss of organic nitrates by aqueous-phase OH oxidation, Atmos. Chem. Phys., 21, 4915–4937, https://doi.org/10.5194/acp-21-4915-2021, 2021.
Guenther, A., Jiang, X., Heald, C. L., Sakulyanontvittaya, T., Duhl, T., Emmons, L., and Wang, X.: The Model of Emissions of Gases and Aerosols from Nature version 2.1 (MEGAN2. 1): an extended and updated framework for modeling biogenic emissions, Geosci. Model. Dev., 5, 1471–1492, https://doi.org/10.5194/gmd-5-1471-2012, 2012.
Hallquist, M., Wenger, J. C., Baltensperger, U., Rudich, Y., Simpson, D., Claeys, M., Dommen, J., Donahue, N. M., George, C., Goldstein, A. H., Hamilton, J. F., Herrmann, H., Hoffmann, T., Iinuma, Y., Jang, M., Jenkin, M. E., Jimenez, J. L., Kiendler-Scharr, A., Maenhaut, W., McFiggans, G., Mentel, T. F., Monod, A., Prévôt, A. S. H., Seinfeld, J. H., Surratt, J. D., Szmigielski, R., and Wildt, J.: The formation, properties and impact of secondary organic aerosol: current and emerging issues, Atmos. Chem. Phys., 9, 5155–5236, https://doi.org/10.5194/acp-9-5155-2009, 2009.
Hart, E. J., Gordon, S., and Thomas, J. K.: A Review of the Radiation Chemistry of Single-Carbon Compounds and Some Reactions of the Hydrated Electron in Aqueous Solution, Radiat. Res., 4, 74–88, 1964.
EPI Suite™: Estimation Program Interface v4.11, https://www.epa.gov/tsca-screening-tools/epi-suitetm-estimation-program-interface, last access: 20 June 2023.
Héral, B., Stierlin, É., Fernandez, X., and Michel, T.: Phytochemicals from the genus Lavandula: a review, Phytochem Rev., 20, 751–771, https://doi.org/10.1007/s11101-020-09719-z, 2021.
Herrmann, H.: Kinetics of aqueous phase reactions relevant for atmospheric chemistry, Chem. Rev., 103, 4691–4716, https://doi.org/10.1021/cr020658q, 2003.
Herrmann, H., Tilgner, A., Barzaghi, P., Majdik, Z., Gligorovski, S., Poulain, L., and Monod, A.: Towards a more detailed description of tropospheric aqueous phase organic chemistry: CAPRAM 3.0, Atmos. Environ., 39, 4351–4363, https://doi.org/10.1016/j.atmosenv.2005.02.016, 2005.
Herrmann, H., Hoffmann, D., Schaefer, T., Bräuer, P., and Tilgner, A.: Tropospheric Aqueous-Phase Free-Radical Chemistry: Radical Sources, Spectra, Reaction Kinetics and Prediction Tools, ChemPhysChem, 11, 3796–3822, https://doi.org/10.1002/cphc.201000533, 2010.
Herrmann, H., Schaefer, T., Tilgner, A., Styler, S. A., Weller, C., Teich, M., and Otto, T.: Tropospheric Aqueous-Phase Chemistry: Kinetics, Mechanisms, and Its Coupling to a Changing Gas Phase, Chem. Rev., 115, 4259–4334, https://doi.org/10.1021/cr500447k, 2015.
Hiura, T., Yoshioka, H., Matsunaga, S. N., Saito, T., Kohyama, T. I., Kusumoto, N., Uchiyama, K., Suyama, Y., and Tsumura, Y.: Diversification of terpenoid emissions proposes a geographic structure based on climate and pathogen composition in Japanese cedar, Sci. Rep., 11, 8307, https://doi.org/10.1038/s41598-021-87810-x, 2021.
Hoffmann, D., Weigert, B., Barzaghi, P., and Herrmann, H.: Reactivity of poly-alcohols towards OH, NO3 and SO
Hunter, J. F., Carrasquillo, A. J., Daumit, K. E., and Kroll, J. H.: Secondary Organic Aerosol Formation from Acyclic, Monocyclic, and Polycyclic Alkanes, Environ. Sci. Technol., 48, 10227–10234, https://doi.org/10.1021/es502674s, 2014.
IUPAC Task Group on Atmospheric Chemical Kinetic Data Evaluation: https://iupac-aeris.ipsl.fr/show_datasheets.php?category=Systematic+OH, last access: 26 September 2023.
Jimenez, J. L., Canagaratna, M. R., Donahue, N. M., Prevot, A. S. H., Zhang, Q., Kroll, J. H., DeCarlo, P. F., Allan, J. D., Coe, H., Ng, N. L., Aiken, A. C., Docherty, K. S., Ulbrich, I. M., Grieshop, A. P., Robinson, A. L., Duplissy, J., Smith, J. D., Wilson, K. R., Lanz, V. A., Hueglin, C., Sun, Y. L., Tian, J., Laaksonen, A., Raatikainen, T., Rautiainen, J., Vaattovaara, P., Ehn, M., Kulmala, M., Tomlinson, J. M., Collins, D. R., Cubison, M. J., Dunlea, J., Huffman, J. A., Onasch, T. B., Alfarra, M. R., Williams, P. I., Bower, K., Kondo, Y., Schneider, J., Drewnick, F., Borrmann, S., Weimer, S., Demerjian, K., Salcedo, D., Cottrell, L., Griffin, R., Takami, A., Miyoshi, T., Hatakeyama, S., Shimono, A., Sun, J. Y., Zhang, Y. M., Dzepina, K., Kimmel, J. R., Sueper, D., Jayne, J. T., Herndon, S. C., Trimborn, A. M., Williams, L. R., Wood, E. C., Middlebrook, A. M., Kolb, C. E., Baltensperger, U., and Worsnop, D. R.: Evolution of Organic Aerosols in the Atmosphere, Science, 326, 1525–1529, https://doi.org/10.1126/science.1180353, 2009.
Klein, R. A.: Hydrogen bonding in diols and binary diol–water systems investigated using DFT methods. II. Calculated infrared OH-stretch frequencies, force constants, and NMR chemical shifts correlate with hydrogen bond geometry and electron density topology. A reevaluation of geometrical criteria for hydrogen bonding, J. Comput. Chem., 24, 1120–1131, https://doi.org/10.1002/jcc.10256, 2003.
Konjeviæ, L., Racar, M., Ilinèiæ, P., and Faraguna, F.: A comprehensive study on application properties of diesel blends with propanol, butanol, isobutanol, pentanol, hexanol, octanol and dodecanol, Energy, 262, 125430, https://doi.org/10.1016/j.energy.2022.125430, 2023.
Kopinke, F.-D. and Georgi, A.: What Controls Selectivity of Hydroxyl Radicals in Aqueous Solution? Indications for a Cage Effect, J. Phys. Chem. A, 121, 7947–7955, https://doi.org/10.1021/acs.jpca.7b05782, 2017.
Krofliè, A., Schaefer, T., Huš, M., Phuoc Le, H., Otto, T., and Herrmann, H.: OH radicals reactivity towards phenol-related pollutants in water: temperature dependence of the rate constants and novel insights into the [OH–phenol]ÿ adduct formation, Phys. Chem. Chem. Phys., 22, 1324–1332, https://doi.org/10.1039/C9CP05533A, 2020.
Kwok, E. S. C. 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, https://doi.org/10.1016/1352-2310(95)00069-B, 1995.
Leviss, D. H., Van Ry, D. A., and Hinrichs, R. Z.: Multiphase Ozonolysis of Aqueous á-Terpineol, Environ. Sci. Technol., 50, 11698–11705, https://doi.org/10.1021/acs.est.6b03612, 2016.
Lim, Y. B. and Ziemann, P. J.: Effects of Molecular Structure on Aerosol Yields from OH Radical-Initiated Reactions of Linear, Branched, and Cyclic Alkanes in the Presence of NOx, Environ. Sci. Technol., 43, 2328–2334, https://doi.org/10.1021/es803389s, 2009.
Lin, G., Sillman, S., Penner, J. E., and Ito, A.: Global modeling of SOA: the use of different mechanisms for aqueous-phase formation, Atmos. Chem. Phys., 14, 5451–5475, https://doi.org/10.5194/acp-14-5451-2014, 2014.
Mahilang, M., Deb, M. K., and Pervez, S.: Biogenic secondary organic aerosols: A review on formation mechanism, analytical challenges and environmental impacts, Chemosphere, 262, 127771, https://doi.org/10.1016/j.chemosphere.2020.127771, 2021.
Matheson, M. S., Mamou, A., Silverman, J., and Rabani, J.: Reaction of hydroxyl radicals with polyethylene oxide in aqueous solution, J. Phys. Chem. , 77, 2420–2424, https://doi.org/10.1021/j100639a011, 1973.
McGillen, Carter, W. P. L., Mellouki, A., Orlando, J. J., Picquet-Varrault, B., and Wallington, T. J.: Database for the kinetics of the gas-phase atmospheric reactions of organic compounds, Earth Syst. Sci. Data, 12, 1203–1216, https://doi.org/10.5194/essd-12-1203-2020, 2020.
McGillen, M. R., Carter, W. P. L., Mellouki, A., Orlando, J. J., Picquet-Varrault, B., and Wallington, T. J.: Database for the Kinetics of the Gas-Phase Atmospheric Reactions of Organic Compounds, Eurochamp Data Center [data set], https://doi.org/10.25326/mh4q-y215, 2021.
McNeill, V. F.: Aqueous Organic Chemistry in the Atmosphere: Sources and Chemical Processing of Organic Aerosols, Environ. Sci. Technol. , 49, 1237–1244, https://doi.org/10.1021/es5043707, 2015.
McVay, R. and Ervens, B.: A microphysical parameterization of aqSOA and sulfate formation in clouds, Geophys. Res. Lett., 44, 7500–7509, https://doi.org/10.1002/2017gl074233, 2017.
Mekic, M. and Gligorovski, S.: Ionic strength effects on heterogeneous and multiphase chemistry: Clouds versus aerosol particles, Atmos. Environ., 244, 117911, https://doi.org/10.1016/j.atmosenv.2020.117911, 2021.
Mellouki, A., Le Bras, G., and Sidebottom, H.: Kinetics and Mechanisms of the Oxidation of Oxygenated Organic Compounds in the Gas Phase, Chem. Rev., 103, 5077–5096, https://doi.org/10.1021/cr020526x, 2003.
Mellouki, A., Wallington, T. J., and Chen, J.: Atmospheric Chemistry of Oxygenated Volatile Organic Compounds: Impacts on Air Quality and Climate, Chem. Rev., 115, 3984–4014, https://doi.org/10.1021/cr500549n, 2015.
Merz, J. H. and Waters, W. A.: A. – Electron-transfer reactions, The mechanism of oxidation of alcohols with Fenton's reagent, Discuss. Faraday Soc., 2, 179–188, https://doi.org/10.1039/DF9470200179, 1947.
Mitroka, S., Zimmeck, S., Troya, D., and Tanko, J. M.: How Solvent Modulates Hydroxyl Radical Reactivity in Hydrogen Atom Abstractions, J. Am. Chem. Soc., 132, 2907–2913, https://doi.org/10.1021/ja903856t, 2010.
Monod, A. and Doussin, J. F.: 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, https://doi.org/10.1016/j.atmosenv.2008.06.005, 2008.
Monod, A., Poulain, L., Grubert, S., Voisin, D., and Wortham, H.: Kinetics of OH-initiated oxidation of oxygenated organic compounds in the aqueous phase: new rate constants, structure–activity relationships and atmospheric implications, Atmos. Environ., 39, 7667–7688, https://doi.org/10.1016/j.atmosenv.2005.03.019, 2005.
Murakami, M. and Ishida, N.: â-Scission of Alkoxy Radicals in Synthetic Transformations, Chem. Lett, 46, 1692–1700, https://doi.org/10.1246/cl.170834, 2017.
Otto, S. and Engberts, J. B. F. N.: Hydrophobic interactions and chemical reactivity, Org. Biomol. Chem., 1, 2809–2820, https://doi.org/10.1039/B305672D, 2003.
Otto, T., Schaefer, T., and Herrmann, H.: Aqueous-Phase Oxidation of Terpene-Derived Acids by Atmospherically Relevant Radicals, J. Phys. Chem. A, 122, 9233–9241, https://doi.org/10.1021/acs.jpca.8b08922, 2018.
Pai, S. J., Heald, C. L., Pierce, J. R., Farina, S. C., Marais, E. A., Jimenez, J. L., Campuzano-Jost, P., Nault, B. A., Middlebrook, A. M., Coe, H., Shilling, J. E., Bahreini, R., Dingle, J. H., and Vu, K.: An evaluation of global organic aerosol schemes using airborne observations, Atmos. Chem. Phys., 20, 2637–2665, https://doi.org/10.5194/acp-20-2637-2020, 2020.
Peduzzi, P., Concato, J., Kemper, E., Holford, T. R., and Feinstein, A. R.: A simulation study of the number of events per variable in logistic regression analysis, J. Clin. Epidemiol., 49, 1373–1379, https://doi.org/10.1016/S0895-4356(96)00236-3, 1996.
Prutz, W. A. and Vogel, S.: Specific rate constants of hydroxyl radical and hydrated electron reaction determined by RCL method, Z. Naturforsch., 31, 1501–1510, https://doi.org/10.1515/znb-1976-1115, 1976.
Pye, H. O. T., Ward-Caviness, C. K., Murphy, B. N., Appel, K. W., and Seltzer, K. M.: Secondary organic aerosol association with cardiorespiratory disease mortality in the United States, Nat. Commun., 12, 7215, https://doi.org/10.1038/s41467-021-27484-1, 2021.
Rauk, A., Boyd, R. J., Boyd, S. L., Henry, D. J., and Radom, L.: Alkoxy radicals in the gaseous phase: â-scission reactions and formation by radical addition to carbonyl compounds, Can. J. Chem., 81, 431–442, https://doi.org/10.1139/v02-206, 2003.
Reuvers, A. P., Greenstock, C. L., Borsa, J., and Chapman, J. D.: Studies on the Mechanism of Chemical Radioprotection by Dimethyl Sulphoxide, Int. J. Radiat. Biol. Relat. Stud. Phys. Chem. Med., 24, 533–536, https://doi.org/10.1080/09553007314551431, 1973.
Richters, S., Herrmann, H., and Berndt, T.: Gas-phase rate coefficients of the reaction of ozone with four sesquiterpenes at 295 ± 2 K, Phys. Chem. Chem. Phys., 17, 11658–11669, https://doi.org/10.1039/C4CP05542J, 2015.
Ross, P. D. and Rekharsky, M. V.: Thermodynamics of hydrogen bond and hydrophobic interactions in cyclodextrin complexes, Biophys. J., 71, 2144–2154, https://doi.org/10.1016/S0006-3495(96)79415-8, 1996.
Russell, G. A.: Deuterium-isotope Effects in the Autoxidation of Aralkyl Hydrocarbons, Mechanism of the Interaction of PEroxy Radicals1, J. Am. Chem. Soc., 79, 3871–3877, https://doi.org/10.1021/ja01571a068, 1957.
Sander, R.: Compilation of Henry's law constants (version 4.0) for water as solvent, Atmos. Chem. Phys., 15, 4399–4981, https://doi.org/10.5194/acp-15-4399-2015, 2015.
Sarang, K., Otto, T., Rudzinski, K., Schaefer, T., Grgiæ, I., Nestorowicz, K., Herrmann, H., and Szmigielski, R.: Reaction Kinetics of Green Leaf Volatiles with Sulfate, Hydroxyl, and Nitrate Radicals in Tropospheric Aqueous Phase, Environ. Sci. Technol., 55, 13666–13676, https://doi.org/10.1021/acs.est.1c03276, 2021.
Sato, K., Jia, T., Tanabe, K., Morino, Y., Kajii, Y., and Imamura, T.: Terpenylic acid and nine-carbon multifunctional compounds formed during the aging of α-pinene ozonolysis secondary organic aerosol, Atmos. Environ., 130, 127–135, https://doi.org/10.1016/j.atmosenv.2015.08.047, 2016.
Schaefer, T., Wen, L., Estelmann, A., Maak, J., and Herrmann, H.: pH- and Temperature-Dependent Kinetics of the Oxidation Reactions of OH with Succinic and Pimelic Acid in Aqueous Solution, Atmosphere, 11, 320–334, https://doi.org/10.3390/atmos11040320, 2020.
Scholes, G. and Willson, R. L.: ã-Radiolysis of aqueous thymine solutions. Determination of relative reaction rates of OH radicals, Trans. Faraday Soc., 63, 2983–2993, https://doi.org/10.1039/TF9676302983, 1967.
Schöne, L., Schindelka, J., Szeremeta, E., Schaefer, T., Hoffmann, D., Rudzinski, K. J., Szmigielski, R., and Herrmann, H.: Atmospheric aqueous phase radical chemistry of the isoprene oxidation products methacrolein, methyl vinyl ketone, methacrylic acid and acrylic acid – kinetics and product studies, Phys. Chem. Chem. Phys., 16, 6257–6272, https://doi.org/10.1039/C3CP54859G, 2014.
Shrivastava, M., Cappa, C. D., Fan, J., Goldstein, A. H., Guenther, A. B., Jimenez, J. L., Kuang, C., Laskin, A., Martin, S. T., Ng, N. L., Petaja, T., Pierce, J. R., Rasch, P. J., Roldin, P., Seinfeld, J. H., Shilling, J., Smith, J. N., Thornton, J. A., Volkamer, R., Wang, J., Worsnop, D. R., Zaveri, R. A., Zelenyuk, A., and Zhang, Q.: Recent advances in understanding secondary organic aerosol: Implications for global climate forcing, Rev. Geophys., 55, 509–559, https://doi.org/10.1002/2016RG000540, 2017.
Sindelarova, K., Granier, C., Bouarar, I., Guenther, A., Tilmes, S., Stavrakou, T., Müller, J. F., Kuhn, U., Stefani, P., and Knorr, W.: Global data set of biogenic VOC emissions calculated by the MEGAN model over the last 30 years, Atmos. Chem. Phys., 14, 9317–9341, https://doi.org/10.5194/acp-14-9317-2014, 2014.
Sindelarova, K., Markova, J., Simpson, D., Huszar, P., Karlicky, J., Darras, S., and Granier, C.: High-resolution biogenic global emission inventory for the time period 2000–2019 for air quality modelling, Earth Syst. Sci. Data, 14, 251–270, https://doi.org/10.5194/essd-14-251-2022, 2022.
Smith, I. W. M. and Ravishankara, A. R.: Role of Hydrogen-Bonded Intermediates in the Bimolecular Reactions of the Hydroxyl Radical, J. Phys. Chem. A, 106, 4798–4807, https://doi.org/10.1021/jp014234w, 2002.
Stemmler, K. and von Gunten, U.: OH radical-initiated oxidation of organic compounds in atmospheric water phases: part 1. Reactions of peroxyl radicals derived from 2-butoxyethanol in water, Atmos. Environ., 34, 4241–4252, https://doi.org/10.1016/S1352-2310(00)00218-1, 2000.
Su, H., Cheng, Y., and Pöschl, U.: New Multiphase Chemical Processes Influencing Atmospheric Aerosols, Air Quality, and Climate in the Anthropocene, Acc. Chem. Res., 53, 2034–2043, https://doi.org/10.1021/acs.accounts.0c00246, 2020.
Swain, C. G. and Lupton, E. C.: Field and resonance components of substituent effects, J. Am. Chem. Soc., 90, 4328–4337, https://doi.org/10.1021/ja01018a024, 1968.
Tsigaridis, K. and Kanakidou, M.: The Present and Future of Secondary Organic Aerosol Direct Forcing on Climate, Curr. Clim. Change Rep., 4, 84–98, https://doi.org/10.1007/s40641-018-0092-3, 2018.
Tsui, W. G., Woo, J. L., and McNeill, V. F.: Impact of Aerosol-Cloud Cycling on Aqueous Secondary Organic Aerosol Formation, Atmosphere, 10, 666–678, https://doi.org/10.3390/atmos10110666, 2019.
von Sonntag, C. and Schuchmann, H.-P.: The Elucidation of Peroxyl Radical Reactions in Aqueous Solution with the Help of Radiation-Chemical Methods, Angew. Chem., Int. Ed. Engl., 30, 1229–1253, https://doi.org/10.1002/anie.199112291, 1991.
Willson, R. L., Greenstock, C. L., Adams, G. E., Wageman, R., and Dorfman, L. M.: The standardization of hydroxyl radical rate data from radiation chemistry, Int. J. Radiat. Phys. Chem., 3, 211–220, https://doi.org/10.1016/0020-7055(71)90023-4, 1971.
Witkowski, B.: Kinetic dataset – aqueous oxidation of aliphatic molecules by hydroxyl radical, RepOD [data set], https://doi.org/10.18150/CPIWK1, 2023.
Witkowski, B. and Gierczak, T.: cis-Pinonic Acid Oxidation by Hydroxyl Radicals in the Aqueous Phase under Acidic and Basic Conditions: Kinetics and Mechanism, Environ. Sci. Technol., 51, 9765–9773, https://doi.org/10.1021/acs.est.7b02427, 2017.
Witkowski, B., Al-sharafi, M., and Gierczak, T.: Kinetics of Limonene Secondary Organic Aerosol Oxidation in the Aqueous Phase, Environ. Sci. Technol., 52, 11583–11590, https://doi.org/10.1021/acs.est.8b02516, 2018a.
Witkowski, B., Jurdana, S., and Gierczak, T.: Limononic Acid Oxidation by Hydroxyl Radicals and Ozone in the Aqueous Phase, Environ. Sci. Technol., 52, 3402–3411, https://doi.org/10.1021/acs.est.7b04867, 2018b.
Witkowski, B., Al-sharafi, M., and Gierczak, T.: Kinetics and products of the aqueous-phase oxidation of â-caryophyllonic acid by hydroxyl radicals, Atmos. Environ., 213, 231–238, https://doi.org/10.1016/j.atmosenv.2019.06.016, 2019.
Witkowski, B., Chi, J., Jain, P., Błaziak, K., and Gierczak, T.: Aqueous OH kinetics of saturated C6–C10 dicarboxylic acids under acidic and basic conditions between 283 and 318 K; new structure-activity relationship parameters, Atmos. Environ., 267, 118761, https://doi.org/10.1016/j.atmosenv.2021.118761, 2021.
Witkowski, B., al-Sharafi, M., Błaziak, K., and Gierczak, T.: Aging of α-Pinene Secondary Organic Aerosol by Hydroxyl Radicals in the Aqueous Phase: Kinetics and Products, Environ. Sci. Technol., 57, 6040–6051, https://doi.org/10.1021/acs.est.2c07630, 2023.
Xu, L., Du, L., Tsona, N. T., and Ge, M.: Anthropogenic Effects on Biogenic Secondary Organic Aerosol Formation, Adv. Atmos. Sci., 38, 1053–1084, https://doi.org/10.1007/s00376-020-0284-3, 2021.
Yamabe, S. and Yamazaki, S.: A DFT study of proton transfers for the reaction of phenol and hydroxyl radical leading to dihydroxybenzene and H2O in the water cluster, Int. J. Quantum Chem., 118, e25510, https://doi.org/10.1002/qua.25510, 2018.
Yasmeen, F., Szmigielski, R., Vermeylen, R., Gómez-González, Y., Surratt, J. D., Chan, A. W. H., Seinfeld, J. H., Maenhaut, W., and Claeys, M.: Mass spectrometric characterization of isomeric terpenoic acids from the oxidation of α-pinene, α-pinene, d-limonene, and Ä3-carene in fine forest aerosol, J. Mass Spectrom., 46, 425–442, https://doi.org/10.1002/jms.1911, 2011.
Zhao, R., Aljawhary, D., Lee, A. K. Y., and Abbatt, J. P. D.: Rapid Aqueous-Phase Photooxidation of Dimers in the α-Pinene Secondary Organic Aerosol, Environ. Sci. Technol. Lett., 4, 205–210, https://doi.org/10.1021/acs.estlett.7b00148, 2017.
Zhou, W., Mekic, M., Liu, J., Loisel, G., Jin, B., Vione, D., and Gligorovski, S.: Ionic strength effects on the photochemical degradation of acetosyringone in atmospheric deliquescent aerosol particles, Atmos. Environ., 198, 83–88, https://doi.org/10.1016/j.atmosenv.2018.10.047, 2019.
Zhu, Y., Tilgner, A., Hoffmann, E. H., Herrmann, H., Kawamura, K., Yang, L., Xue, L., and Wang, W.: Multiphase MCM–CAPRAM modeling of the formation and processing of secondary aerosol constituents observed during the Mt. Tai summer campaign in 2014, Atmos. Chem. Phys., 20, 6725–6747, https://doi.org/10.5194/acp-20-6725-2020, 2020.
Short summary
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.
This article reports the results of the kinetic measurements for the aqueous oxidation of the 29...
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