Articles | Volume 21, issue 19
https://doi.org/10.5194/acp-21-15003-2021
© Author(s) 2021. 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-21-15003-2021
© Author(s) 2021. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
08 Oct 2021
Research article |
| 08 Oct 2021
| 08 Oct 2021
An organic crystalline state in ageing atmospheric aerosol proxies: spatially resolved structural changes in levitated fatty acid particles
Adam Milsom
School of Geography, Earth and
Environmental Sciences, University of Birmingham, Edgbaston, B15 2TT, Birmingham, UK
Adam M. Squires
Department of Chemistry, University of Bath, South Building,
Soldier Down Ln, Claverton Down, BA2 7AX, Bath, UK
Jacob A. Boswell
Department of Chemistry, University of Bath, South Building,
Soldier Down Ln, Claverton Down, BA2 7AX, Bath, UK
Nicholas J. Terrill
Diamond Light Source, Diamond House, Harwell Science and Innovation
Campus, OX11 0DE, Didcot, UK
Andrew D. Ward
Central Laser Facility, Rutherford Appleton Laboratory, Harwell
Campus, OX11 0QX, Didcot, UK
School of Geography, Earth and
Environmental Sciences, University of Birmingham, Edgbaston, B15 2TT, Birmingham, UK
Department of Meteorology, University of Reading, Whiteknights,
Earley Gate, RG6 6BB, Reading, UK
Related authors
Sophie A. Mills, Adam Milsom, Christian Pfrang, A. Rob MacKenzie, and Francis D. Pope
Atmos. Meas. Tech., 16, 4885–4898, https://doi.org/10.5194/amt-16-4885-2023, https://doi.org/10.5194/amt-16-4885-2023, 2023
Short summary
Short summary
Pollen grains are important components of the atmosphere and have the potential to impact upon cloud processes via their ability to help in the formation of rain droplets. This study investigates the hygroscopicity of two different pollen species using an acoustic levitator. Pollen grains are levitated, and their response to changes in relative humidity is investigated. A key advantage of this method is that it is possible study pollen shape under varying environmental conditions.
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
Short summary
Short summary
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.
Adam Milsom, Amy Lees, Adam M. Squires, and Christian Pfrang
Geosci. Model Dev., 15, 7139–7151, https://doi.org/10.5194/gmd-15-7139-2022, https://doi.org/10.5194/gmd-15-7139-2022, 2022
Short summary
Short summary
MultilayerPy is a Python-based framework facilitating the creation, running and optimisation of state-of-the-art kinetic multi-layer models of aerosol and film processes. Models can be fit to data with local and global optimisation algorithms along with a statistical sampling algorithm, which quantifies the uncertainty in optimised model parameters. This “modelling study in a box” enables more reproducible and reliable results, with model code and outputs produced in a human-readable way.
Adam Milsom, Adam M. Squires, Andrew D. Ward, and Christian Pfrang
Atmos. Chem. Phys., 22, 4895–4907, https://doi.org/10.5194/acp-22-4895-2022, https://doi.org/10.5194/acp-22-4895-2022, 2022
Short summary
Short summary
Cooking emissions can self-organise into nanostructured lamellar bilayers, and this can influence reaction kinetics. We developed a kinetic multi-layer model-based description of decay data we obtained from laboratory experiments of the ozonolysis of coated films of such a self-organised system, demonstrating a decreased diffusivity for both oleic acid and ozone. Nanostructure formation can thus increase the reactive half-life of oleic acid by days under typical indoor and outdoor conditions.
Benjamin Woden, Maximilian W. A. Skoda, Adam Milsom, Curtis Gubb, Armando Maestro, James Tellam, and Christian Pfrang
Atmos. Chem. Phys., 21, 1325–1340, https://doi.org/10.5194/acp-21-1325-2021, https://doi.org/10.5194/acp-21-1325-2021, 2021
Short summary
Short summary
Atmospheric aerosols contain a large amount of organic compounds, whose oxidation affects their physical properties through a process known as ageing. We have simulated atmospheric ageing experimentally to elucidate the nature and behaviour of residual surface films. Our results show an increasing amount of residue at near-zero temperatures, demonstrating that an inert product film may build up during droplet ageing, even if only ordinarily short-lived reactive species are initially emitted.
Adam Milsom, Adam M. Squires, Ben Laurence, Ben Wōden, Andrew J. Smith, Andrew D. Ward, and Christian Pfrang
EGUsphere, https://doi.org/10.5194/egusphere-2024-905, https://doi.org/10.5194/egusphere-2024-905, 2024
This preprint is open for discussion and under review for Atmospheric Chemistry and Physics (ACP).
Short summary
Short summary
We followed nano-structural changes in mixtures found in urban organic aerosol emissions (oleic acid, sodium oleate & fructose) during humidity change & ozone exposure. We demonstrate that self-assembly of fatty acid nanostructures can impact on water uptake & chemical reactivity affecting atmospheric lifetimes, urban air quality (protecting harmful emissions from degradation and enabling their long-range transport) & climate (affecting cloud formation) with implications for human health.
Sophie A. Mills, Adam Milsom, Christian Pfrang, A. Rob MacKenzie, and Francis D. Pope
Atmos. Meas. Tech., 16, 4885–4898, https://doi.org/10.5194/amt-16-4885-2023, https://doi.org/10.5194/amt-16-4885-2023, 2023
Short summary
Short summary
Pollen grains are important components of the atmosphere and have the potential to impact upon cloud processes via their ability to help in the formation of rain droplets. This study investigates the hygroscopicity of two different pollen species using an acoustic levitator. Pollen grains are levitated, and their response to changes in relative humidity is investigated. A key advantage of this method is that it is possible study pollen shape under varying environmental conditions.
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
Short summary
Short summary
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.
Adam Milsom, Amy Lees, Adam M. Squires, and Christian Pfrang
Geosci. Model Dev., 15, 7139–7151, https://doi.org/10.5194/gmd-15-7139-2022, https://doi.org/10.5194/gmd-15-7139-2022, 2022
Short summary
Short summary
MultilayerPy is a Python-based framework facilitating the creation, running and optimisation of state-of-the-art kinetic multi-layer models of aerosol and film processes. Models can be fit to data with local and global optimisation algorithms along with a statistical sampling algorithm, which quantifies the uncertainty in optimised model parameters. This “modelling study in a box” enables more reproducible and reliable results, with model code and outputs produced in a human-readable way.
Adam Milsom, Adam M. Squires, Andrew D. Ward, and Christian Pfrang
Atmos. Chem. Phys., 22, 4895–4907, https://doi.org/10.5194/acp-22-4895-2022, https://doi.org/10.5194/acp-22-4895-2022, 2022
Short summary
Short summary
Cooking emissions can self-organise into nanostructured lamellar bilayers, and this can influence reaction kinetics. We developed a kinetic multi-layer model-based description of decay data we obtained from laboratory experiments of the ozonolysis of coated films of such a self-organised system, demonstrating a decreased diffusivity for both oleic acid and ozone. Nanostructure formation can thus increase the reactive half-life of oleic acid by days under typical indoor and outdoor conditions.
Benjamin Woden, Maximilian W. A. Skoda, Adam Milsom, Curtis Gubb, Armando Maestro, James Tellam, and Christian Pfrang
Atmos. Chem. Phys., 21, 1325–1340, https://doi.org/10.5194/acp-21-1325-2021, https://doi.org/10.5194/acp-21-1325-2021, 2021
Short summary
Short summary
Atmospheric aerosols contain a large amount of organic compounds, whose oxidation affects their physical properties through a process known as ageing. We have simulated atmospheric ageing experimentally to elucidate the nature and behaviour of residual surface films. Our results show an increasing amount of residue at near-zero temperatures, demonstrating that an inert product film may build up during droplet ageing, even if only ordinarily short-lived reactive species are initially emitted.
Mohammed S. Alam, Leigh R. Crilley, James D. Lee, Louisa J. Kramer, Christian Pfrang, Mónica Vázquez-Moreno, Milagros Ródenas, Amalia Muñoz, and William J. Bloss
Atmos. Meas. Tech., 13, 5977–5991, https://doi.org/10.5194/amt-13-5977-2020, https://doi.org/10.5194/amt-13-5977-2020, 2020
Short summary
Short summary
We report on the interference arising in measurements of nitrogen oxides (NOx) from the presence of a range of alkenes in sampled air when using the most widespread air quality monitoring technique for chemiluminescence detection. Interferences of up to 11 % are reported, depending upon the alkene present and conditions used. Such interferences may be of substantial importance for the interpretation of ambient NOx data, particularly for high volatile organic compound and low NOx environments.
Rosalie H. Shepherd, Martin D. King, Amelia A. Marks, Neil Brough, and Andrew D. Ward
Atmos. Chem. Phys., 18, 5235–5252, https://doi.org/10.5194/acp-18-5235-2018, https://doi.org/10.5194/acp-18-5235-2018, 2018
Short summary
Short summary
The refractive index of atmospheric extracts sourced from urban (London), remote (Antarctica), and woodsmoke aerosol was determined by applying optical trapping simultaneously with Mie spectroscopy. In addition, owing to the absorbing nature of woodsmoke and an aqueous humic acid aerosol extract, the absorption Ångström exponent could be determined.The refractive index and absorption Ångström exponent were then applied in a top-of-the-atmosphere albedo radiation transfer model.
Federica Sebastiani, Richard A. Campbell, Kunal Rastogi, and Christian Pfrang
Atmos. Chem. Phys., 18, 3249–3268, https://doi.org/10.5194/acp-18-3249-2018, https://doi.org/10.5194/acp-18-3249-2018, 2018
Short summary
Short summary
We report the first kinetic study of a key atmospheric nighttime oxidant (NO3) with one-molecule thin organic layers at the air–water interface. Organic molecules were chosen to establish the impact of head group, aliphatic chain length and saturation. We show that NO3 may dominate degradation at night, retention of the organic character varies strongly and atmospheric lifetimes are longer than those determined at the interface – a key motivation for further experimental and modelling studies.
Related subject area
Subject: Aerosols | Research Activity: Laboratory Studies | Altitude Range: Troposphere | Science Focus: Chemistry (chemical composition and reactions)
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
Technical Note: A Technique to Convert NO2 to NO2– with S(IV) and its Application to Measuring Nitrate Photolysis
Suppressed atmospheric chemical aging of cooking organic aerosol particles in wintertime conditions
Bulk and molecular-level composition of primary organic aerosol from wood, straw, cow dung, and plastic burning
Formation and Loss of Light Absorbance by Phenolic Aqueous SOA by OH and an Organic Triplet Excited State
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
Impact of fossil and non-fossil fuel sources on the molecular compositions of water-soluble humic-like substances in PM2.5 at a suburban site of Yangtze River Delta, China
Technical note: Improved synthetic routes to cis- and trans-(2-methyloxirane-2,3-diyl)dimethanol (cis- and trans-β-isoprene epoxydiol)
Technical note: Intercomparison study of the elemental carbon radiocarbon analysis methods using synthetic known samples
Chemical evolution of primary and secondary biomass burning aerosols during daytime and nighttime
Formation of highly oxygenated organic molecules from the oxidation of limonene by OH radical: significant contribution of H-abstraction pathway
Measurement report: Atmospheric aging of combustion-derived particles – impact on stable free radical concentration and its ability to produce reactive oxygen species in aqueous media
Photoaging of phenolic secondary organic aerosol in the aqueous phase: evolution of chemical and optical properties and effects of oxidants
An intercomparison study of four different techniques for measuring the chemical composition of nanoparticles
Simultaneous formation of sulfate and nitrate via co-uptake of SO2 and NO2 by aqueous NaCl droplets: combined effect of nitrate photolysis and chlorine chemistry
Photo-induced shrinking of aqueous glycine aerosol droplets
Sulfate formation via aerosol-phase SO2 oxidation by model biomass burning photosensitizers: 3,4-dimethoxybenzaldehyde, vanillin and syringaldehyde using single-particle mixing-state analysis
Yields and molecular composition of gas-phase and secondary organic aerosol from the photooxidation of the volatile consumer product benzyl alcohol: formation of highly oxygenated and hydroxy nitro-aromatic compounds
A combined gas- and particle-phase analysis of highly oxygenated organic molecules (HOMs) from α-pinene ozonolysis
Comparison of aqueous secondary organic aerosol (aqSOA) product distributions from guaiacol oxidation by non-phenolic and phenolic methoxybenzaldehydes as photosensitizers in the absence and presence of ammonium nitrate
Technical note: Chemical composition and source identification of fluorescent components in atmospheric water-soluble brown carbon by excitation–emission matrix spectroscopy with parallel factor analysis – potential limitations and applications
Insoluble lipid film mediates transfer of soluble saccharides from the sea to the atmosphere: the role of hydrogen bonding
Magnetic fraction of the atmospheric dust in Kraków – physicochemical characteristics and possible environmental impact
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
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.
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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.
Aaron Lieberman, Julietta Picco, Murat Onder, and Cort Anastasio
EGUsphere, https://doi.org/10.5194/egusphere-2023-2876, https://doi.org/10.5194/egusphere-2023-2876, 2023
Short summary
Short summary
We developed a method that uses S(IV) in aqueous solution to quantitatively convert NO2 to NO2–. This allows both species to be quantified using the Griess method. As an example of the utility of the method, we used it to quantify 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.
Wenli Liu, Longkun He, Yingjun Liu, Keren Liao, Qi Chen, and Mikinori Kuwata
EGUsphere, https://doi.org/10.5194/egusphere-2023-2657, https://doi.org/10.5194/egusphere-2023-2657, 2023
Short summary
Short summary
Cooking is one of the major particle sources in urban areas. Previous laboratory studies demonstrated the chemical lifetimes of cooking organic aerosols 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.
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
Short summary
Short summary
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.
Stephanie Arciva, Lan Ma, Camille Mavis, Chrystal Guzman, and Cort Anastasio
EGUsphere, https://doi.org/10.5194/egusphere-2023-2719, https://doi.org/10.5194/egusphere-2023-2719, 2023
Short summary
Short summary
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.
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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.
Mengying Bao, Yan-Lin Zhang, Fang Cao, Yihang Hong, Yu-Chi Lin, Mingyuan Yu, Hongxing Jiang, Zhineng Cheng, Rongshuang Xu, and Xiaoying Yang
Atmos. Chem. Phys., 23, 8305–8324, https://doi.org/10.5194/acp-23-8305-2023, https://doi.org/10.5194/acp-23-8305-2023, 2023
Short summary
Short summary
The interaction between the sources and molecular compositions of humic-like substances (HULIS) at Nanjing, China, was explored. Significant fossil fuel source contributions to HULIS were found in the 14C results from biomass burnng and traffic emissions. Increasing biogenic secondary organic aerosol (SOA) products and anthropogenic aromatic compounds were detected in summer and winter, respectively.
Molly Frauenheim, Jason D. Surratt, Zhenfa Zhang, and Avram Gold
Atmos. Chem. Phys., 23, 7859–7866, https://doi.org/10.5194/acp-23-7859-2023, https://doi.org/10.5194/acp-23-7859-2023, 2023
Short summary
Short summary
We report synthesis of the isoprene-derived photochemical oxidation products trans- and cis-β-epoxydiols in high overall yields from inexpensive, readily available starting compounds. Protection/deprotection steps or time-consuming purification is not required, and the reactions can be scaled up to gram quantities. The procedures provide accessibility of these important compounds to atmospheric chemistry laboratories with only basic capabilities in organic synthesis.
Xiangyun Zhang, Jun Li, Sanyuan Zhu, Junwen Liu, Ping Ding, Shutao Gao, Chongguo Tian, Yingjun Chen, Ping'an Peng, and Gan Zhang
Atmos. Chem. Phys., 23, 7495–7502, https://doi.org/10.5194/acp-23-7495-2023, https://doi.org/10.5194/acp-23-7495-2023, 2023
Short summary
Short summary
The results show that 14C elemental carbon (EC) was not only related to the isolation method but also to the types and proportions of the biomass sources in the sample. The hydropyrolysis (Hypy) method, which can be used to isolate a highly stable portion of ECHypy and avoid charring, is a more effective and stable approach for the matrix-independent 14C quantification of EC in aerosols, and the 13C–ECHypy and non-fossil ECHypy values of SRM1649b were –24.9 ‰ and 11 %, respectively.
Amir Yazdani, Satoshi Takahama, John K. Kodros, Marco Paglione, Mauro Masiol, Stefania Squizzato, Kalliopi Florou, Christos Kaltsonoudis, Spiro D. Jorga, Spyros N. Pandis, and Athanasios Nenes
Atmos. Chem. Phys., 23, 7461–7477, https://doi.org/10.5194/acp-23-7461-2023, https://doi.org/10.5194/acp-23-7461-2023, 2023
Short summary
Short summary
Organic aerosols directly emitted from wood and pellet stove combustion are found to chemically transform (approximately 15 %–35 % by mass) under daytime aging conditions simulated in an environmental chamber. A new marker for lignin-like compounds is found to degrade at a different rate than previously identified biomass burning markers and can potentially provide indication of aging time in ambient samples.
Hao Luo, Luc Vereecken, Hongru Shen, Sungah Kang, Iida Pullinen, Mattias Hallquist, Hendrik Fuchs, Andreas Wahner, Astrid Kiendler-Scharr, Thomas F. Mentel, and Defeng Zhao
Atmos. Chem. Phys., 23, 7297–7319, https://doi.org/10.5194/acp-23-7297-2023, https://doi.org/10.5194/acp-23-7297-2023, 2023
Short summary
Short summary
Oxidation of limonene, an element emitted by trees and chemical products, by OH, a daytime oxidant, forms many highly oxygenated organic molecules (HOMs), including C10-20 compounds. HOMs play an important role in new particle formation and growth. HOM formation can be explained by the chemistry of peroxy radicals. We found that a minor branching ratio initial pathway plays an unexpected, significant role. Considering this pathway enables accurate simulations of HOMs and other concentrations.
Heather L. Runberg and Brian J. Majestic
Atmos. Chem. Phys., 23, 7213–7223, https://doi.org/10.5194/acp-23-7213-2023, https://doi.org/10.5194/acp-23-7213-2023, 2023
Short summary
Short summary
Environmentally persistent free radicals (EPFRs) are an emerging pollutant found in soot particles. Understanding how these change as they move through the atmosphere is important to human health. Here, soot was generated in the laboratory and exposed to simulated sunlight. The concentrations and characteristics of EPFRs in the soot were measured and found to be unchanged. However, it was also found that the ability of soot to form hydroxyl radicals was stronger for fresh soot.
Wenqing Jiang, Christopher Niedek, Cort Anastasio, and Qi Zhang
Atmos. Chem. Phys., 23, 7103–7120, https://doi.org/10.5194/acp-23-7103-2023, https://doi.org/10.5194/acp-23-7103-2023, 2023
Short summary
Short summary
We studied how aqueous-phase secondary organic aerosol (aqSOA) form and evolve from a phenolic carbonyl commonly present in biomass burning smoke. The composition and optical properties of the aqSOA are significantly affected by photochemical reactions and are dependent on the oxidants' concentration and identity in water. During photoaging, the aqSOA initially becomes darker, but prolonged aging leads to the formation of volatile products, resulting in significant mass loss and photobleaching.
Lucía Caudillo, Mihnea Surdu, Brandon Lopez, Mingyi Wang, Markus Thoma, Steffen Bräkling, Angela Buchholz, Mario Simon, Andrea C. Wagner, Tatjana Müller, Manuel Granzin, Martin Heinritzi, Antonio Amorim, David M. Bell, Zoé Brasseur, Lubna Dada, Jonathan Duplissy, Henning Finkenzeller, Xu-Cheng He, Houssni Lamkaddam, Naser G. A. Mahfouz, Vladimir Makhmutov, Hanna E. Manninen, Guillaume Marie, Ruby Marten, Roy L. Mauldin, Bernhard Mentler, Antti Onnela, Tuukka Petäjä, Joschka Pfeifer, Maxim Philippov, Ana A. Piedehierro, Birte Rörup, Wiebke Scholz, Jiali Shen, Dominik Stolzenburg, Christian Tauber, Ping Tian, António Tomé, Nsikanabasi Silas Umo, Dongyu S. Wang, Yonghong Wang, Stefan K. Weber, André Welti, Marcel Zauner-Wieczorek, Urs Baltensperger, Richard C. Flagan, Armin Hansel, Jasper Kirkby, Markku Kulmala, Katrianne Lehtipalo, Douglas R. Worsnop, Imad El Haddad, Neil M. Donahue, Alexander L. Vogel, Andreas Kürten, and Joachim Curtius
Atmos. Chem. Phys., 23, 6613–6631, https://doi.org/10.5194/acp-23-6613-2023, https://doi.org/10.5194/acp-23-6613-2023, 2023
Short summary
Short summary
In this study, we present an intercomparison of four different techniques for measuring the chemical composition of nanoparticles. The intercomparison was performed based on the observed chemical composition, calculated volatility, and analysis of the thermograms. We found that the methods generally agree on the most important compounds that are found in the nanoparticles. However, they do see different parts of the organic spectrum. We suggest potential explanations for these differences.
Ruifeng Zhang and Chak Keung Chan
Atmos. Chem. Phys., 23, 6113–6126, https://doi.org/10.5194/acp-23-6113-2023, https://doi.org/10.5194/acp-23-6113-2023, 2023
Short summary
Short summary
Research into sulfate and nitrate formation from co-uptake of NO2 and SO2, especially under irradiation, is rare. We studied the co-uptake of NO2 and SO2 by NaCl droplets under various conditions, including irradiation and dark, and RHs, using Raman spectroscopy flow cell and kinetic model simulation. Significant nitrate formation from NO2 hydrolysis can be photolyzed to generate OH radicals that can further react with chloride to produce reactive chlorine species and promote sulfate formation.
Shinnosuke Ishizuka, Oliver Reich, Grégory David, and Ruth Signorell
Atmos. Chem. Phys., 23, 5393–5402, https://doi.org/10.5194/acp-23-5393-2023, https://doi.org/10.5194/acp-23-5393-2023, 2023
Short summary
Short summary
Photosensitizers play an important role in the photochemistry of atmospheric aerosols. Our study provides evidence that mesoscopic glycine clusters forming in aqueous droplets act as unconventional photosensitizers in the visible light spectrum. We observed the influence of these photoactive molecular aggregates in single optically trapped aqueous droplets. Such mesoscopic photosensitizers might be more important for aerosol photochemistry than previously anticipated.
Liyuan Zhou, Zhancong Liang, Beatrix Rosette Go Mabato, Rosemarie Ann Infante Cuevas, Rongzhi Tang, Mei Li, Chunlei Cheng, and Chak K. Chan
Atmos. Chem. Phys., 23, 5251–5261, https://doi.org/10.5194/acp-23-5251-2023, https://doi.org/10.5194/acp-23-5251-2023, 2023
Short summary
Short summary
This study reveals the sulfate formation in photosensitized particles from biomass burning under UV and SO2, of which the relative atmospheric importance in sulfate production was qualitatively compared to nitrate photolysis. On the basis of single-particle aerosol mass spectrometry measurements, the number percentage of sulfate-containing particles and relative peak area of sulfate in single-particle spectra exhibited a descending order of 3,4-dimethoxybenzaldehyde > vanillin > syringaldehyde.
Mohammed Jaoui, Kenneth S. Docherty, Michael Lewandowski, and Tadeusz E. Kleindienst
Atmos. Chem. Phys., 23, 4637–4661, https://doi.org/10.5194/acp-23-4637-2023, https://doi.org/10.5194/acp-23-4637-2023, 2023
Short summary
Short summary
VCPs are a class of chemicals widely used in industrial and consumer products (e.g., coatings, adhesives, inks, personal care products) and are an important component of total VOCs in urban atmospheres. This study provides SOA yields and detailed chemical analysis of the gas- and aerosol-phase products of the photooxidation of one of these VCPs, benzyl alcohol. These results will allow better links between characterized sources and their resulting criteria for pollutant formation.
Jian Zhao, Ella Häkkinen, Frans Graeffe, Jordan E. Krechmer, Manjula R. Canagaratna, Douglas R. Worsnop, Juha Kangasluoma, and Mikael Ehn
Atmos. Chem. Phys., 23, 3707–3730, https://doi.org/10.5194/acp-23-3707-2023, https://doi.org/10.5194/acp-23-3707-2023, 2023
Short summary
Short summary
Based on the combined measurements of gas- and particle-phase highly oxygenated organic molecules (HOMs) from α-pinene ozonolysis, enhancement of dimers in particles was observed. We conducted experiments wherein the dimer to monomer (D / M) ratios of HOMs in the gas phase were modified (adding CO / NO) to investigate the effects of the corresponding D / M ratios in the particles. These results are important for a better understanding of secondary organic aerosol formation in the atmosphere.
Beatrix Rosette Go Mabato, Yong Jie Li, Dan Dan Huang, Yalin Wang, and Chak K. Chan
Atmos. Chem. Phys., 23, 2859–2875, https://doi.org/10.5194/acp-23-2859-2023, https://doi.org/10.5194/acp-23-2859-2023, 2023
Short summary
Short summary
We compared non-phenolic and phenolic methoxybenzaldehydes as photosensitizers for aqueous secondary organic aerosol (aqSOA) formation under cloud and fog conditions. We showed that the structural features of photosensitizers affect aqSOA formation. We also elucidated potential interactions between photosensitization and ammonium nitrate photolysis. Our findings are useful for evaluating the importance of photosensitized reactions on aqSOA formation, which could improve aqSOA predictive models.
Tao Cao, Meiju Li, Cuncun Xu, Jianzhong Song, Xingjun Fan, Jun Li, Wanglu Jia, and Ping'an Peng
Atmos. Chem. Phys., 23, 2613–2625, https://doi.org/10.5194/acp-23-2613-2023, https://doi.org/10.5194/acp-23-2613-2023, 2023
Short summary
Short summary
This work comprehensively investigated the fluorescence data of light-absorbing organic compounds, water-soluble organic matter in different types of aerosol samples, soil dust, and fulvic and humic acids using an excitation–emission matrix (EEM) method and parallel factor modeling. The results revealed which light-absorbing species can be detected by EEM and also provided important information for identifying the chemical composition and possible sources of these species in atmospheric samples.
Minglan Xu, Narcisse Tsona Tchinda, Jianlong Li, and Lin Du
Atmos. Chem. Phys., 23, 2235–2249, https://doi.org/10.5194/acp-23-2235-2023, https://doi.org/10.5194/acp-23-2235-2023, 2023
Short summary
Short summary
The promotion of soluble saccharides on sea spray aerosol (SSA) generation and the changes in particle morphology were observed. On the contrary, the coexistence of surface insoluble fatty acid film and soluble saccharides significantly inhibited the production of SSA. This is the first demonstration that hydrogen bonding mediated by surface-insoluble fatty acids contributes to saccharide transfer in seawater, providing a new mechanism for saccharide enrichment in SSA.
Jan M. Michalik, Wanda Wilczyńska-Michalik, Łukasz Gondek, Waldemar Tokarz, Jan Żukrowski, Marta Gajewska, and Marek Michalik
Atmos. Chem. Phys., 23, 1449–1464, https://doi.org/10.5194/acp-23-1449-2023, https://doi.org/10.5194/acp-23-1449-2023, 2023
Short summary
Short summary
The magnetic fraction of the aerosols in Kraków was collected and analysed using scanning and transmission electron microscopy with energy-dispersive spectrometry, X-ray diffraction, Mössbauer spectrometry, and magnetometry. It contains metallic Fe or Fe-rich alloy and Fe oxides. The occurrence of nanometre-scale Fe3O4 particles (predominantly of anthropogenic origin) is shown. Our results can help to determine the sources and transport of pollutants, potential harmful effects, etc.
Cited articles
Abbatt, J. P. D., Lee, A. K. Y., and Thornton, J. A.: Quantifying trace gas
uptake to tropospheric aerosol: Recent advances and remaining challenges,
Chem. Soc. Rev., 41, 6555–6581, https://doi.org/10.1039/c2cs35052a, 2012.
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.
Allan, J. D., Williams, P. I., Morgan, W. T., Martin, C. L., Flynn, M. J., Lee, J., Nemitz, E., Phillips, G. J., Gallagher, M. W., and Coe, H.: Contributions from transport, solid fuel burning and cooking to primary organic aerosols in two UK cities, Atmos. Chem. Phys., 10, 647–668, https://doi.org/10.5194/acp-10-647-2010, 2010.
Alves, C. A., Vicente, E. D., Evtyugina, M., Vicente, A. M., Nunes, T.,
Lucarelli, F., Calzolai, G., Nava, S., Calvo, A. I., Alegre, C. del B.,
Oduber, F., Castro, A., and Fraile, R.: Indoor and outdoor air quality: A
university cafeteria as a case study, Atmos. Pollut. Res., 11, 531–544,
https://doi.org/10.1016/j.apr.2019.12.002, 2020.
Ananthapadmanabhan, K. P. and Somasundaran, P.: Acid-soap formation in
aqueous oleate solutions, J. Colloid Interface Sci., 122, 104–109,
https://doi.org/10.1016/0021-9797(88)90293-7, 1988.
Athanasiadis, A., Fitzgerald, C., Davidson, N. M., Giorio, C., Botchway, S.
W., Ward, A. D., Kalberer, M., Pope, F. D., and Kuimova, M. K.: Dynamic
viscosity mapping of the oxidation of squalene aerosol particles, Phys.
Chem. Chem. Phys., 18, 30385–30393, https://doi.org/10.1039/c6cp05674a, 2016.
Bastelberger, S., Krieger, U. K., Luo, B. P., and Peter, T.: Time evolution
of steep diffusion fronts in highly viscous aerosol particles measured with
Mie resonance spectroscopy, J. Chem. Phys., 149, 244506,
https://doi.org/10.1063/1.5052216, 2018.
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,
https://doi.org/10.1039/c6cp00634e, 2016.
Blöchliger, E., Blocher, M., Walde, P., and Luisi, P. L.: Matrix Effect
in the Size Distribution of Fatty Acid Vesicles, J. Phys. Chem. B, 102,
10383–10390, https://doi.org/10.1021/jp981234w, 1998.
Boucher, O., Randall, D., Artaxo, P., Bretherton, C., Feingold, G., Forster,
P., Kerminen, V.-M., Kondo, Y., Liao, H., Lohmann, U., Rasch, P., Satheesh,
S. K., Sherwood, S., Stevens, B., and Zhang, X. Y.: Clouds and Aerosols, in:
Climate Change 2013 the Physical Science Basis: Working Group I Contribution
to the Fifth Assessment Report of the Intergovernmental Panel on Climate
Change, edited by: Stocker, T. F., Qin, D., Plattner, G.-K., Tignor, M., Allen, S. K.,
Boschung, J., Nauels, A., Xia, Y., Bex, V., and Midgley, P. M.,
Cambridge University Press, Cambridge, United Kingdom and New
York, NY, USA, 571–658, 2013.
Bzdek, B. R., Reid, J. P., Malila, J., and Prisle, N. L.: The surface tension
of surfactant-containing, finite volume droplets, P. Natl. Acad. Sci. USA, 117, 8335–8343, https://doi.org/10.1073/pnas.1915660117, 2020.
Chan, C. K. and Yao, X.: Air pollution in mega cities in China, Atmos.
Environ., 42, 1–42, https://doi.org/10.1016/j.atmosenv.2007.09.003, 2008.
Cheng, Y., Li, S. M., Leithead, A., Brickell, P. C., and Leaitch, W. R.:
Characterizations of cis-pinonic acid and n-fatty acids on fine aerosols in
the Lower Fraser Valley during Pacific 2001 Air Quality Study, Atmos.
Environ., 38, 5789–5800, https://doi.org/10.1016/j.atmosenv.2004.01.051, 2004.
Chu, S. N., Sands, S., Tomasik, M. R., Lee, P. S., and McNeill, V. F.: Ozone
oxidation of surface-adsorbed polycyclic aromatic hydrocarbons: Role of
PAH-surface interaction, J. Am. Chem. Soc., 132, 15968–15975,
https://doi.org/10.1021/ja1014772, 2010.
Cistola, D. P., Atkinson, D., Hamilton, J. A., and Small, D. M.: Phase
Behavior and Bilayer Properties of Fatty Acids: Hydrated 1:1 Acid-Soaps,
Biochemistry, 25, 2804–2812, https://doi.org/10.1021/bi00358a011, 1986.
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,
https://doi.org/10.1021/acs.analchem.5b04315, 2016.
Engblom, J., Engström, S. and Fontell, K.: The effect of the skin
penetration enhancer Azone® on fatty acid-sodium soap-water
mixtures, J. Control. Release, 33, 299–305,
https://doi.org/10.1016/0168-3659(94)00105-4, 1995.
Estillore, A. D., Trueblood, J. V., and Grassian, V. H.: Atmospheric
chemistry of bioaerosols: Heterogeneous and multiphase reactions with
atmospheric oxidants and other trace gases, Chem. Sci., 7, 6604–6616,
https://doi.org/10.1039/c6sc02353c, 2016.
Facchini, M. C., Mircea, M., Fuzzi, S., and Charlson, R. J.: Cloud albedo
enhancement by surface-active organic solutes in growing droplets, Nature,
401, 257–259, https://doi.org/10.1038/45758, 1999.
Facchini, M. C., Decesari, S., Mircea, M., Fuzzi, S., and Loglio, G.: Surface
tension of atmospheric wet aerosol and cloud/fog droplets in relation to
their organic carbon content and chemical composition, Atmos. Environ.,
34, 4853–4857, https://doi.org/10.1016/S1352-2310(00)00237-5, 2000.
Fitzgerald, C., Hosny, N. A., Tong, H., Seville, P. C., Gallimore, P. J.,
Davidson, N. M., Athanasiadis, A., Botchway, S. W., Ward, A. D., Kalberer,
M., Kuimova, M. K., and Pope, F. D.: Fluorescence lifetime imaging of
optically levitated aerosol: A technique to quantitatively map the viscosity
of suspended aerosol particles, Phys. Chem. Chem. Phys., 18,
21710–21719, https://doi.org/10.1039/c6cp03674k, 2016.
Freedman, M. A.: Phase separation in organic aerosol, Chem. Soc. Rev.,
46, 7694–7705, https://doi.org/10.1039/c6cs00783j, 2017.
Freedman, M. A.: Liquid–Liquid Phase Separation in Supermicrometer and
Submicrometer Aerosol Particles, Acc. Chem. Res., 53, 1102–1110,
https://doi.org/10.1021/acs.accounts.0c00093, 2020.
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.
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., Griffiths, P. T., Pope, F. D., Reid, J. P., and Kalberer,
M.: Comprehensive modeling study of ozonolysis of oleic acid aerosol based
on real-time, online measurements of aerosol composition, J. Geophys. Res.,
122, 4364–4377, https://doi.org/10.1002/2016JD026221, 2017.
Guarnieri, M. and Balmes, J. R.: Outdoor air pollution and asthma, Lancet,
383, 1581–1592, https://doi.org/10.1016/S0140-6736(14)60617-6, 2014.
He, X., Leng, C., Pang, S., and Zhang, Y.: Kinetics study of heterogeneous
reactions of ozone with unsaturated fatty acid single droplets using
micro-FTIR spectroscopy, RSC Adv., 7, 3204–3213, https://doi.org/10.1039/C6RA25255A,
2017.
Hosny, N. A., Fitzgerald, C., Tong, C., Kalberer, M., Kuimova, M. K., and
Pope, F. D.: Fluorescent lifetime imaging of atmospheric aerosols: A direct
probe of aerosol viscosity, Faraday Discuss., 165, 343–356,
https://doi.org/10.1039/c3fd00041a, 2013.
Hosny, N. A., Fitzgerald, C., Vyšniauskas, A., Athanasiadis, A.,
Berkemeier, T., Uygur, N., Pöschl, U., Shiraiwa, M., Kalberer, M., Pope,
F. D., and Kuimova, M. K.: Direct imaging of changes in aerosol particle
viscosity upon hydration and chemical aging, Chem. Sci., 7, 1357–1367,
https://doi.org/10.1039/c5sc02959g, 2016.
Hung, H. M., Katrib, Y., and Martin, S. T.: Products and mechanisms of the
reaction of oleic acid with ozone and nitrate radical, J. Phys. Chem. A,
109, 4517–4530, https://doi.org/10.1021/jp0500900, 2005.
Ishimaru, M., Toyota, T., Takakura, K., Sugawara, T., and Sugawara, Y.:
Helical Aggregate of Oleic Acid and Its Dynamics in Water at pH 8, Chem.
Lett., 34, 46–47, https://doi.org/10.1246/cl.2005.46, 2005.
Iwahashi, M., Yamaguchi, Y., Kato, T., Horiuchi, T., Sakurai, I., and Suzuki,
M.: Temperature dependence of molecular conformation and liquid structure of
cis-9-octadecenoic acid, J. Phys. Chem., 95, 445–451,
https://doi.org/10.1021/j100154a078, 1991.
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.
Kanakidou, M., Seinfeld, J. H., Pandis, S. N., Barnes, I., Dentener, F. J., Facchini, M. C., Van Dingenen, R., Ervens, B., Nenes, A., Nielsen, C. J., Swietlicki, E., Putaud, J. P., Balkanski, Y., Fuzzi, S., Horth, J., Moortgat, G. K., Winterhalter, R., Myhre, C. E. L., Tsigaridis, K., Vignati, E., Stephanou, E. G., and Wilson, J.: Organic aerosol and global climate modelling: a review, Atmos. Chem. Phys., 5, 1053–1123, https://doi.org/10.5194/acp-5-1053-2005, 2005.
Kang, M., Yang, F., Ren, H., Zhao, W., Zhao, Y., Li, L., Yan, Y., Zhang, Y.,
Lai, S., Zhang, Y., Yang, Y., Wang, Z., Sun, Y. and Fu, P.: Influence of
continental organic aerosols to the marine atmosphere over the East China
Sea: Insights from lipids, PAHs and phthalates, Sci. Total Environ.,
607–608, 339–350, https://doi.org/10.1016/j.scitotenv.2017.06.214, 2017.
Keene, W. C., Pszenny, A. A. P., Maben, J. R., Stevenson, E., and Wall, A.:
Closure evaluation of size-resolved aerosol pH in the New England coastal
atmosphere during summer, J. Geophys. Res.-Atmos., 109, 1–16,
https://doi.org/10.1029/2004JD004801, 2004.
King, M. D., Thompson, K. C., and Ward, A. D.: Laser tweezers raman study of
optically trapped aerosol droplets of seawater and oleic acid reacting with
ozone: Implications for cloud-droplet properties, J. Am. Chem. Soc.,
126, 16710–16711, https://doi.org/10.1021/ja044717o, 2004.
King, M. D., Rennie, A. R., Thompson, K. C., Fisher, F. N., Dong, C. C.,
Thomas, R. K., Pfrang, C. and Hughes, A. V.: Oxidation of oleic acid at the
air-water interface and its potential effects on cloud critical
supersaturations, Phys. Chem. Chem. Phys., 11(35), 7699–7707,
https://doi.org/10.1039/b906517b, 2009.
King, M. D., Rennie, A. R., Pfrang, C., Hughes, A. V., and Thompson, K. C.:
Interaction of nitrogen dioxide (NO2) with a monolayer of oleic acid at the
air-water interface – A simple proxy for atmospheric aerosol, Atmos.
Environ., 44, 1822–1825, https://doi.org/10.1016/j.atmosenv.2010.01.031, 2010.
Kirpes, R. M., Bonanno, D., May, N. W., Fraund, M., Barget, A. J., Moffet,
R. C., Ault, A. P. and Pratt, K. A.: Wintertime Arctic Sea Spray Aerosol
Composition Controlled by Sea Ice Lead Microbiology, ACS Cent. Sci., 5(11),
1760–1767, https://doi.org/10.1021/acscentsci.9b00541, 2019.
Knopf, D. A., Anthony, L. M., and Bertram, A. K.: Reactive uptake of O3 by
multicomponent and multiphase mixtures containing oleic acid, J. Phys. Chem.
A, 109, 5579–5589, https://doi.org/10.1021/jp0512513, 2005.
Koop, T., Bookhold, J., Shiraiwa, M., and Pöschl, U.: Glass transition
and phase state of organic compounds: Dependency on molecular properties and
implications for secondary organic aerosols in the atmosphere, Phys. Chem.
Chem. Phys., 13, 19238–19255, https://doi.org/10.1039/c1cp22617g, 2011.
Laskin, A., Moffet, R. C., and Gilles, M. K.: Chemical Imaging of Atmospheric
Particles, Acc. Chem. Res., 52, 3419–3431,
https://doi.org/10.1021/acs.accounts.9b00396, 2019.
Last, D. J., Nájera, J. J., Wamsley, R., Hilton, G., McGillen, M.,
Percival, C. J., and Horn, A. B.: Ozonolysis of organic compounds and
mixtures in solution, Part I: Oleic, maleic, nonanoic and benzoic acids,
Phys. Chem. Chem. Phys., 11, 1427–1440, https://doi.org/10.1039/b815425b, 2009.
Lee, J. W. L., Carrascón, V., Gallimore, P. J., Fuller, S. J.,
Björkegren, A., Spring, D. R., Pope, F. D., and Kalberer, M.: The effect
of humidity on the ozonolysis of unsaturated compounds in aerosol particles,
Phys. Chem. Chem. Phys., 14, 8023–8031, https://doi.org/10.1039/c2cp24094g, 2012.
Liao, H., Seinfeld, J. H., Adams, P. J., and Mickley, L. J.: Global radiative
forcing of coupled tropospheric ozone and aerosols in a unified general
circulation model, J. Geophys. Res.-Atmos., 109, 1–33,
https://doi.org/10.1029/2003JD004456, 2004.
Lisiecki, I., André, P., Filankembo, A., Petit, C., Tanori, J.,
Gulik-Krzywicki, T., Ninham, B. W., and Pileni, M. P.: Mesostructured fluids,
1. Cu(AOT)2-H2O-isooctane in oil rich regions, J. Phys. Chem. B, 103,
9168–9175, https://doi.org/10.1021/jp991242s, 1999.
Liu, P., Song, M., Zhao, T., Gunthe, S. S., Ham, S., He, Y., Qin, Y. M.,
Gong, Z., Amorim, J. C., Bertram, A. K., and Martin, S. T.: Resolving the
mechanisms of hygroscopic growth and cloud condensation nuclei activity for
organic particulate matter, Nat. Commun., 9, 4076,
https://doi.org/10.1038/s41467-018-06622-2, 2018.
Lynch, M. L.: Acid-soaps, Curr. Opin. Colloid Interface Sci., 2,
495–500, https://doi.org/10.1016/S1359-0294(97)80097-0, 1997.
Lynch, M. L., Pan, Y., and Laughlin, R. G.: Spectroscopic and thermal
characterization of 1:2 sodium soap/fatty acid acid-soap crystals, J. Phys.
Chem., 100, 357–361, https://doi.org/10.1021/jp952124h, 1996.
Lynch, M. L., Wireko, F., Tarek, M., and Klein, M.: Intermolecular
Interactions and the Structure of Fatty Acid−Soap Crystals, J. Phys. Chem.
B, 105, 552–561, https://doi.org/10.1021/jp002602a, 2002.
Marshall, F. H., Miles, R. E. H., Song, Y., Ohm, P. B., Power, R. M., Reid,
J. P., and Dutcher, C. S.: Diffusion and reactivity in ultraviscous aerosol
and the correlation with particle viscosity, Chem. Sci., 7, 1298–1308,
https://doi.org/10.1039/c5sc03223g, 2016.
Mauersberger, K., Barnes, J., Hanson, D., and Morton, J.: Measurement of the
ozone absorption cross-section at the 253.7 nm mercury line, Geophys. Res.
Lett., 13, 671–673, https://doi.org/10.1029/GL013i007p00671, 1986.
Mele, S., Söderman, O., Ljusberg-Wahrén, H., Thuresson, K.,
Monduzzi, M., and Nylander, T.: Phase behavior in the biologically important
oleic acid/sodium oleate/water system, Chem. Phys. Lipids, 211, 30–36, https://doi.org/10.1016/j.chemphyslip.2017.11.017, 2018.
Mendez, M., Visez, N., Gosselin, S., Crenn, V., Riffault, V., and Petitprez,
D.: Reactive and nonreactive ozone uptake during aging of oleic acid
particles, J. Phys. Chem. A, 118, 9471–9481, https://doi.org/10.1021/jp503572c,
2014.
Mezzenga, R., Meyer, C., Servais, C., Romoscanu, A. I., Sagalowicz, L., and
Hayward, R. C.: Shear rheology of lyotropic liquid crystals: A case study,
Langmuir, 21, 3322–3333, https://doi.org/10.1021/la046964b, 2005.
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.
Milsom, A., Squires, A. M., Woden, B., Terrill, N. J., Ward, A. D., and
Pfrang, C.: The persistence of a proxy for cooking emissions in megacities:
a kinetic study of the ozonolysis of self-assembled films by simultaneous
small and wide angle X-ray scattering (SAXS/WAXS) and Raman microscopy,
Faraday Discuss., 226, 364–381, https://doi.org/10.1039/D0FD00088D, 2021a.
Milsom, A., Squires, A. M., Boswell, J., Terrill, N. J., Ward, A. D.,
Pfrang, C., Data supporting the study “An organic crystalline state in
ageing atmospheric aerosol proxies: spatially resolved structural changes in
levitated fatty acid particles” by Milsom et al. (2021), Zenodo [data set],
https://doi.org/10.5281/zenodo.5471408, 2021b.
Moise, T. and Rudich, Y.: Reactive uptake of ozone by aerosol-associated
unsaturated fatty acids: Kinetics, mechanism, and products, J. Phys. Chem.
A, 106, 6469–6476, https://doi.org/10.1021/jp025597e, 2002.
Morris, J. W., Davidovits, P., Jayne, J. T., Jimenez, J. L., Shi, Q., Kolb,
C. E., Worsnop, D. R., Barney, W. S., and Cass, G.: Kinetics of submicron
oleic acid aerosols with ozone: A novel aerosol mass spectrometric
technique, Geophys. Res. Lett., 29, 1357, https://doi.org/10.1029/2002gl014692,
2002.
Mu, Q., Shiraiwa, M., Octaviani, M., Ma, N., Ding, A., Su, H., Lammel, G.,
Pöschl, U., and Cheng, Y.: Temperature effect on phase state and
reactivity controls atmospheric multiphase chemistry and transport of PAHs,
Sci. Adv., 4, eaap7314, https://doi.org/10.1126/sciadv.aap7314, 2018.
Nájera, J. J., Percival, C. J., and Horn, A. B.: Infrared spectroscopic
evidence for a heterogeneous reaction between ozone and sodium oleate at the
gas-aerosol interface: Effect of relative humidity, Int. J. Chem. Kinet.,
47, 277–288, https://doi.org/10.1002/kin.20907, 2015.
Nikiforidis, C. V., Gilbert, E. P., and Scholten, E.: Organogel formation via
supramolecular assembly of oleic acid and sodium oleate, RSC Adv., 5,
47466–47475, https://doi.org/10.1039/c5ra05336f, 2015.
Osterroht, C.: Extraction of dissolved fatty acids from sea water,
Fresenius, J. Anal. Chem., 345, 773–779, https://doi.org/10.1007/BF00323009, 1993.
Ots, R., Vieno, M., Allan, J. D., Reis, S., Nemitz, E., Young, D. E., Coe, H., Di Marco, C., Detournay, A., Mackenzie, I. A., Green, D. C., and Heal, M. R.: Model simulations of cooking organic aerosol (COA) over the UK using estimates of emissions based on measurements at two sites in London, Atmos. Chem. Phys., 16, 13773–13789, https://doi.org/10.5194/acp-16-13773-2016, 2016.
Ovadnevaite, J., Zuend, A., Laaksonen, A., Sanchez, K. J., Roberts, G.,
Ceburnis, D., Decesari, S., Rinaldi, M., Hodas, N., Facchini, M. C.,
Seinfeld, J. H., and O'Dowd, C.: Surface tension prevails over solute effect
in organic-influenced cloud droplet activation, Nature, 546, 637–641,
https://doi.org/10.1038/nature22806, 2017.
Panich, N. M. and Ershov, B. G.: Solubility of Ozone in Organic Solvents,
Russ. J. Gen. Chem., 89, 185–189, https://doi.org/10.1134/S1070363219020026, 2019.
Paglione, M., Decesari, S., Rinaldi, M., Tarozzi, L., Manarini, F.,
Gilardoni, S., Facchini, M. C., Fuzzi, S., Bacco, D., Trentini, A., Pandis,
S. N., and Nenes, A.: Historical Changes in Seasonal Aerosol Acidity in the
Po Valley (Italy) as Inferred from Fog Water and Aerosol Measurements,
Environ. Sci. Technol., 55, 7307–7315, https://doi.org/10.1021/acs.est.1c00651, 2021.
Pfrang, C., Shiraiwa, M., and Pöschl, U.: Chemical ageing and transformation of diffusivity in semi-solid multi-component organic aerosol particles, Atmos. Chem. Phys., 11, 7343–7354, https://doi.org/10.5194/acp-11-7343-2011, 2011.
Pfrang, C., Sebastiani, F., Lucas, C. O. M., King, M. D., Hoare, I. D.,
Chang, D., and Campbell, R. A.: Ozonolysis of methyl oleate monolayers at the
air-water interface: Oxidation kinetics, reaction products and atmospheric
implications, Phys. Chem. Chem. Phys., 16, 13220–13228,
https://doi.org/10.1039/c4cp00775a, 2014.
Pfrang, C., Rastogi, K., Cabrera-Martinez, E. R., Seddon, A. M., Dicko, C.,
Labrador, A., Plivelic, T. S., Cowieson, N., and Squires, A. M.: Complex
three-dimensional self-assembly in proxies for atmospheric aerosols, Nat.
Commun., 8, 1724, https://doi.org/10.1038/s41467-017-01918-1, 2017.
Pöschl, U.: Atmospheric aerosols: Composition, transformation, climate
and health effects, Angew. Chemie Int. Ed., 44, 7520–7540,
https://doi.org/10.1002/anie.200501122, 2005.
Price, H. C., Mattsson, J., Zhang, Y., Bertram, A. K., Davies, J. F.,
Grayson, J. W., Martin, S. T., O'Sullivan, D., Reid, J. P., Rickards, A. M.
J., and Murray, B. J.: Water diffusion in atmospherically relevant α-pinene secondary organic material, Chem. Sci., 6, 4876–4883,
https://doi.org/10.1039/c5sc00685f, 2015.
Prisle, N. L., Asmi, A., Topping, D., Partanen, A.-I., Romakkaniemi, S., Dal
Maso, M., Kulmala, M., Laaksonen, A., Lehtinen, K. E. J., McFiggans, G., and
Kokkola, H.: Surfactant effects in global simulations of cloud droplet
activation, Geophys. Res. Lett., 39, L05802, https://doi.org/10.1029/2011GL050467,
2012.
Putnam, C. D., Hammel, M., Hura, G. L., and Tainer, J. A.: X-ray solution
scattering (SAXS) combined with crystallography and computation: defining
accurate macromolecular structures, conformations and assemblies in
solution, Q. Rev. Biophys., 40, 191–285, https://doi.org/10.1017/s0033583507004635,
2007.
Reid, J. P., Bertram, A. K., Topping, D. O., Laskin, A., Martin, S. T.,
Petters, M. D., Pope, F. D., and Rovelli, G.: The viscosity of
atmospherically relevant organic particles, Nat. Commun., 9, 1–14,
https://doi.org/10.1038/s41467-018-03027-z, 2018.
Renbaum-Wolff, L., Grayson, J. W., Bateman, A. P., Kuwata, M., Sellier, M.,
Murray, B. J., Shilling, J. E., Martin, S. T., and Bertram, A. K.: Viscosity
of a-pinene secondary organic material and implications for particle growth
and reactivity, P. Natl. Acad. Sci. USA, 110, 8014–8019,
https://doi.org/10.1073/pnas.1219548110, 2013.
Reynolds, J. C., Last, D. J., McGillen, M., Nijs, A., Horn, A. B., Percival,
C., Carpenter, L. J., and Lewis, A. C.: Structural analysis of oligomeric
molecules formed from the reaction products of oleic acid ozonolysis,
Environ. Sci. Technol., 40, 6674–6681, https://doi.org/10.1021/es060942p, 2006.
Robinson, A. L., Donahue, N. M., and Rogge, W. F.: Photochemical oxidation
and changes in molecular composition of organic aerosol in the regional
context, J. Geophys. Res. Atmos., 111, 1–15, https://doi.org/10.1029/2005JD006265,
2006.
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, https://doi.org/10.1146/annurev.physchem.58.032806.104432, 2007.
Salentinig, S., Sagalowicz, L., and Glatter, O.: Self-Assembled Structures
and pKa Value of Oleic Acid in Systems of Biological Relevance, Langmuir,
26, 11670–11679, https://doi.org/10.1021/la101012a, 2010.
Schwier, A. N., Sareen, N., Lathem, T. L., Nenes, A., and McNeill, V. F.:
Ozone oxidation of oleic acid surface films decreases aerosol cloud
condensation nuclei activity, J. Geophys. Res.-Atmos., 116, D16202,
https://doi.org/10.1029/2010JD015520, 2011.
Sebastiani, F., Campbell, R. A., Rastogi, K., and Pfrang, C.: Nighttime oxidation of surfactants at the air–water interface: effects of chain length, head group and saturation, Atmos. Chem. Phys., 18, 3249–3268, https://doi.org/10.5194/acp-18-3249-2018, 2018.
Seddon, A. M., Richardson, S. J., Rastogi, K., Plivelic, T. S., Squires, A.
M., and Pfrang, C.: Control of Nanomaterial Self-Assembly in Ultrasonically
Levitated Droplets, J. Phys. Chem. Lett., 7, 1341–1345,
https://doi.org/10.1021/acs.jpclett.6b00449, 2016.
Seddon, J. M., Bartle, E. A., and Mingins, J.: Inverse cubic
liquid-crystalline phases of phospholipids and related lyotropic systems, J.
Phys. Condens. Matter, 2, 285–290, https://doi.org/10.1088/0953-8984/2/S/043, 1990.
Shiraiwa, M., Pfrang, C., and Pöschl, U.: Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone, Atmos. Chem. Phys., 10, 3673–3691, https://doi.org/10.5194/acp-10-3673-2010, 2010.
Shiraiwa, M., Ammann, M., Koop, T., and Poschl, U.: Gas uptake and chemical
aging of semisolid organic aerosol particles, P. Natl. Acad. Sci. USA, 108, 11003–11008, https://doi.org/10.1073/pnas.1103045108, 2011.
Shiraiwa, M., Li, Y., Tsimpidi, A. P., Karydis, V. A., Berkemeier, T.,
Pandis, S. N., Lelieveld, J., Koop, T., and Pöschl, U.: Global
distribution of particle phase state in atmospheric secondary organic
aerosols, Nat. Commun., 8, 1–7, https://doi.org/10.1038/ncomms15002, 2017.
Shrivastava, M., Lou, S., Zelenyuk, A., Easter, R. C., Corley, R. A.,
Thrall, B. D., Rasch, P. J., Fast, J. D., Simonich, S. L. M., Shen, H., and
Tao, S.: Global long-range transport and lung cancer risk from polycyclic
aromatic hydrocarbons shielded by coatings of organic aerosol, P. Natl. Acad. Sci. USA, 114, 1246–1251, https://doi.org/10.1073/pnas.1618475114, 2017.
Slade, J. H., Ault, A. P., Bui, A. T., Ditto, J. C., Lei, Z., Bondy, A. L.,
Olson, N. E., Cook, R. D., Desrochers, S. J., Harvey, R. M., Erickson, M.
H., Wallace, H. W., Alvarez, S. L., Flynn, J. H., Boor, B. E., Petrucci, G.
A., Gentner, D. R., Griffin, R. J., and Shepson, P. B.: Bouncier Particles at
Night: Biogenic Secondary Organic Aerosol Chemistry and Sulfate Drive Diel
Variations in the Aerosol Phase in a Mixed Forest, Environ. Sci. Technol.,
53, 4977–4987, https://doi.org/10.1021/acs.est.8b07319, 2019.
Smith, G. D., Woods, E., DeForest, C. L., Baer, T., and Miller, R. E.:
Reactive uptake of ozone by oleic acid aerosol particles: Application of
single-particle mass spectrometry to heterogeneous reaction kinetics, J.
Phys. Chem. A, 106, 8085–8095, https://doi.org/10.1021/jp020527t, 2002.
Stevens, B. and Feingold, G.: Untangling aerosol effects on clouds and
precipitation in a buffered system, Nature, 461, 607–613,
https://doi.org/10.1038/nature08281, 2009.
Tabazadeh, A.: Organic aggregate formation in aerosols and its impact on the
physicochemical properties of atmospheric particles, Atmos. Environ.,
39, 5472–5480, https://doi.org/10.1016/j.atmosenv.2005.05.045, 2005.
Tandon, P., Raudenkolb, S., Neubert, R. H. H., Rettig, W., and Wartewig, S.:
X-ray diffraction and spectroscopic studies of oleic acid-sodium oleate,
Chem. Phys. Lipids, 109, 37–45, https://doi.org/10.1016/S0009-3084(00)00207-3, 2001.
Tervahattu, H.: Identification of an organic coating on marine aerosol
particles by TOF-SIMS, J. Geophys. Res., 107, 4319,
https://doi.org/10.1029/2001JD001403, 2002.
Tervahattu, H., Juhanoja, J., Vaida, V., Tuck, A. F., Niemi, J. V.,
Kupiainen, K., Kulmala, M., and Vehkamäki, H.: Fatty acids on continental
sulfate aerosol particles, J. Geophys. Res.-Atmos., 110(6), 1–9,
https://doi.org/10.1029/2004JD005400, 2005.
Tiddy, G. J. T.: Surfactant-water liquid crystal phases, Phys. Rep., 57,
1–46, https://doi.org/10.1016/0370-1573(80)90041-1, 1980.
Tuckermann, R.: Surface tension of aqueous solutions of water-soluble
organic and inorganic compounds, Atmos. Environ., 41, 6265–6275,
https://doi.org/10.1016/j.atmosenv.2007.03.051, 2007.
Veghte, D. P., Altaf, M. B., and Freedman, M. A.: Size dependence of the
structure of organic aerosol, J. Am. Chem. Soc., 135, 16046–16049,
https://doi.org/10.1021/ja408903g, 2013.
Vesna, O., Sax, M., Kalberer, M., Gaschen, A., and Ammann, M.: Product study
of oleic acid ozonolysis as function of humidity, Atmos. Environ., 43,
3662–3669, https://doi.org/10.1016/j.atmosenv.2009.04.047, 2009.
Vicente, E. D., Vicente, A., Evtyugina, M., Carvalho, R., Tarelho, L. A. C.,
Oduber, F. I., and Alves, C.: Particulate and gaseous emissions from charcoal
combustion in barbecue grills, Fuel Process. Technol., 176, 296–306,
https://doi.org/10.1016/j.fuproc.2018.03.004, 2018.
Virtanen, A., Joutsensaari, J., Koop, T., Kannosto, J., Yli-Pirilä, P.,
Leskinen, J., Mäkelä, J. M., Holopainen, J. K., Pöschl, U.,
Kulmala, M., Worsnop, D. R., and Laaksonen, A.: An amorphous solid state of
biogenic secondary organic aerosol particles, Nature, 467, 824–827,
https://doi.org/10.1038/nature09455, 2010.
Wang, M., Yao, L., Zheng, J., Wang, X., Chen, J., Yang, X., Worsnop, D. R.,
Donahue, N. M., and Wang, L.: Reactions of Atmospheric Particulate Stabilized
Criegee Intermediates Lead to High-Molecular-Weight Aerosol Components,
Environ. Sci. Technol., 50, 5702–5710, https://doi.org/10.1021/acs.est.6b02114,
2016.
Woden, B., Skoda, M., Hagreen, M., and Pfrang, C.: Night-Time Oxidation of a
Monolayer Model for the Air–Water Interface of Marine Aerosols – A Study by
Simultaneous Neutron Reflectometry and in Situ Infra-Red Reflection
Absorption Spectroscopy (IRRAS), Atmosphere (Basel), 9, 471,
https://doi.org/10.3390/atmos9120471, 2018.
Woden, B., Skoda, M. W. A., Milsom, A., Gubb, C., Maestro, A., Tellam, J., and Pfrang, C.: Ozonolysis of fatty acid monolayers at the air–water interface: organic films may persist at the surface of atmospheric aerosols, Atmos. Chem. Phys., 21, 1325–1340, https://doi.org/10.5194/acp-21-1325-2021, 2021.
Zabara, A. and Mezzenga, R.: Controlling molecular transport and sustained
drug release in lipid-based liquid crystalline mesophases, J. Control.
Release, 188, 31–43, https://doi.org/10.1016/j.jconrel.2014.05.052, 2014.
Zahardis, J. and Petrucci, G. A.: The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system – a review, Atmos. Chem. Phys., 7, 1237–1274, https://doi.org/10.5194/acp-7-1237-2007, 2007.
Zahardis, J., LaFranchi, B. W., and Petrucci, G. A.: Photoelectron resonance
capture ionization-aerosol mass spectrometry of the ozonolysis products of
oleic acid particles: Direct measure of higher molecular weight oxygenates,
J. Geophys. Res.-Atmos., 110, 1–10, https://doi.org/10.1029/2004JD005336, 2005.
Zahardis, J., LaFranchi, B. W., and Petrucci, G. A.: Direct observation of
polymerization in the oleic acid-ozone heterogeneous reaction system by
photoelectron resonance capture ionization aerosol mass spectrometry, Atmos.
Environ., 40, 1661–1670, https://doi.org/10.1016/j.atmosenv.2005.10.065, 2006.
Zhang, Q., Jimenez, J. L., Worsnop, D. R., and Canagaratna, M.: A case study
of urban particle acidity and its influence on secondary organic aerosol,
Environ. Sci. Technol., 41, 3213–3219, https://doi.org/10.1021/es061812j, 2007.
Zhao, X., Hu, Q., Wang, X., Ding, X., He, Q., Zhang, Z., Shen, R., Lü,
S., Liu, T., Fu, X., and Chen, L.: Composition profiles of organic aerosols
from Chinese residential cooking: Case study in urban Guangzhou, south
China, J. Atmos. Chem., 72, 1–18, https://doi.org/10.1007/s10874-015-9298-0, 2015.
Zhou, S., Hwang, B. C. H., Lakey, P. S. J., Zuend, A., Abbatt, J. P. D., and
Shiraiwa, M.: Multiphase reactivity of polycyclic aromatic hydrocarbons is
driven by phase separation and diffusion limitations, P. Natl. Acad. Sci. USA, 116, 11658–11663, https://doi.org/10.1073/pnas.1902517116, 2019.
Zobrist, B., Soonsin, V., Luo, B. P., Krieger, U. K., Marcolli, C., Peter,
T., and Koop, T.: Ultra-slow water diffusion in aqueous sucrose glasses,
Phys. Chem. Chem. Phys., 13, 3514–3526, https://doi.org/10.1039/c0cp01273d, 2011.
Short summary
Atmospheric aerosols can be solid, semi-solid or liquid. This phase state may impact key aerosol processes such as oxidation and water uptake, affecting cloud droplet formation and urban air pollution. We have observed a solid crystalline organic phase in a levitated proxy for cooking emissions, oleic acid. Spatially resolved structural changes were followed during ageing by X-ray scattering, revealing phase gradients, aggregate products and a markedly reduced ozonolysis reaction rate.
Atmospheric aerosols can be solid, semi-solid or liquid. This phase state may impact key aerosol...
Altmetrics
Final-revised paper
Preprint