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Photolytically induced changes in composition and volatility of biogenic secondary organic aerosol from nitrate radical oxidation during night-to-day transition
Stockholm University, Faculty of Science, Department of Environmental Science.
Stockholm University, Faculty of Science, Department of Environmental Science.
Stockholm University, Faculty of Science, Department of Environmental Science.ORCID iD: 000-0003-2985-4846
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Number of Authors: 132021 (English)In: Atmospheric Chemistry And Physics, ISSN 1680-7316, E-ISSN 1680-7324, Vol. 21, no 19, p. 14907-14925Article in journal (Refereed) Published
Abstract [en]

Night-time reactions of biogenic volatile organic compounds (BVOCs) and nitrate radicals (NO3) can lead to the formation of NO3-initiated biogenic secondary organic aerosol (BSOANO3). Here, we study the impacts of light exposure on the chemical composition and volatility of BSOANO3 formed in the dark from three precursors (isoprene, α-pinene, and β-caryophyllene) in atmospheric simulation chamber experiments. Our study represents BSOANO3 formation conditions where reactions between peroxy radicals (RO2 + RO2) and between RO2 and NO3 are favoured. The emphasis here is on the identification of particle-phase organonitrates (ONs) formed in the dark and their changes during photolytic ageing on timescales of ∼ 1 h. The chemical composition of particle-phase compounds was measured with a chemical ionization mass spectrometer with a filter inlet for gases and aerosols (FIGAERO-CIMS) and an extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF). Volatility information on BSOANO3 was derived from FIGAERO-CIMS desorption profiles (thermograms) and a volatility tandem differential mobility analyser (VTDMA). During photolytic ageing, there was a relatively small change in mass due to evaporation (< 5 % for the isoprene and α-pinene BSOANO3, and 12 % for the β-caryophyllene BSOANO3), but we observed significant changes in the chemical composition of the BSOANO3. Overall, 48 %, 44 %, and 60 % of the respective total signal for the isoprene, α-pinene, and β-caryophyllene BSOANO3 was sensitive to photolytic ageing and exhibited decay. The photolabile compounds include both monomers and oligomers. Oligomers can decompose into their monomer units through photolysis of the bonds (e.g. likely O–O) between them. Fragmentation of both oligomers and monomers also happened at other positions, causing the formation of compounds with shorter carbon skeletons. The cleavage of the nitrate functional group from the carbon chain was likely not a main degradation pathway in our experiments. In addition, photolytic degradation of compounds changes their volatility and can lead to evaporation. We use different methods to assess bulk volatilities and discuss their changes during both dark ageing and photolysis in the context of the chemical changes that we observed. We also reveal large uncertainties in saturation vapour pressure estimated from parameterizations for the ON oligomers with multiple nitrate groups. Overall, our results suggest that photolysis causes photodegradation of a substantial fraction of BSOANO3, changes both the chemical composition and the bulk volatility of the particles, and might be a potentially important loss pathway of BSOANO3 during the night-to-day transition.

Place, publisher, year, edition, pages
2021. Vol. 21, no 19, p. 14907-14925
National Category
Earth and Related Environmental Sciences
Identifiers
URN: urn:nbn:se:su:diva-198816DOI: 10.5194/acp-21-14907-2021ISI: 000706062500001OAI: oai:DiVA.org:su-198816DiVA, id: diva2:1611944
Available from: 2021-11-16 Created: 2021-11-16 Last updated: 2025-02-07Bibliographically approved
In thesis
1. Insights into key processes governing atmospheric aerosol loadings and their interactions with clouds
Open this publication in new window or tab >>Insights into key processes governing atmospheric aerosol loadings and their interactions with clouds
2022 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Aerosol particles are ubiquitous in the atmosphere and an essential part of the atmospheric radiation balance regulating the Earth’s temperature. Aerosol-cloud interaction still remains the largest single uncertainty in future climate projections. In addition, aerosols are also responsible for air pollution, causing severe health effects. With various origins and short atmospheric lifetimes, aerosols are unevenly distributed in the atmosphere, making simulations of air pollution and future climate scenarios challenging. This thesis aims to improve the understanding of the physical and chemical processes that govern aerosol concentration in the atmosphere, using both field as well as laboratory experiments.

Field measurements were performed at a remote station at Mt Åreskutan, central Sweden. Located at 1250 m a.s.l. the station is frequently covered by clouds, allowing for in-cloud measurements. Aerosol particle size distribution measurements revealed a shift towards smaller diameters in the ambient aerosol size distribution after the station had been within a cloud. This is a result of the larger (> 60 nm) particles being more effectively scavenged by clouds as compared with the smaller end of the size distribution. Chemical analysis revealed a similar composition of the cloud water as the particulate matter, suggesting that cloud droplet activation at Mt Åreskutan is primarily dependent on particle size, and the aerosol population to have been internally mixed. Similarly, measurement of hygroscopicity and volatility revealed similar water-solubility and evaporation behaviour for the ambient aerosols and cloud residuals, with the organic fraction representative of aged boreal secondary organic aerosol (SOA) and showing no signs of significant aqueous phase processing.

The NArVE laboratory campaign took place in an atmospheric simulation chamber at Paul Scherrer Institute, Switzerland. The experiments traced nitrate-induced SOA formation and ageing of three biogenic precursors, namely α-pinene, isoprene, and β-caryophyllene, using mass spectrometric techniques and evaporation measurements. The volatility of α-pinene SOA from nitrate oxidation was found to be higher than the corresponding ozonolysis products. The nitrate oxidation of isoprene resulted in species with similar volatility to α-pinene, while the β-caryophyllene system produced lower volatility compounds then the other two precursors. Quantitative comparison of the volatility measurements to commonly-used theoretical parameterizations revealed the need for further studies of the impact of the nitrate functional group on molecular volatility. Dark ageing of α-pinene was found to mainly occur through particle phase oxidation forming less volatile species. During the photolysis related to sunrise the molecular composition changed towards more volatile species, while no significant evaporation could be observed for the α-pinene and isoprene systems.

A common theme in all these studies was investigating the level of detail needed to theoretically describe the observations. We found that while simple approximations (such as internal mixing and size-independent chemical composition of the particles) are often sufficient to capture trends in atmospheric aerosol properties, more research on (1) the processes taking place on shorter time- and smaller size scales than investigated here and (2) the effects of nitrate group on molecular volatility are warranted.

Place, publisher, year, edition, pages
Stockholm: Department of Environmental Science, Stockholm University, 2022. p. 36
National Category
Meteorology and Atmospheric Sciences Environmental Sciences
Research subject
Applied Environmental Science
Identifiers
urn:nbn:se:su:diva-202484 (URN)978-91-7911-804-4 (ISBN)978-91-7911-805-1 (ISBN)
Public defence
2022-04-13, De Geersalen, Geovetenskapens hus, Svante Arrhenius väg 14 and online via Zoom, public link is available at the department website, Stockholm, 09:00 (English)
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Available from: 2022-03-21 Created: 2022-02-28 Last updated: 2025-02-01Bibliographically approved

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Wu, ChengGraham, Emelie L.Haslett, SophieRiipinen, IlonaPrevot, Andre S. H.Mohr, Claudia

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