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Enrichment of biogenic and anthropogenic organic substances on sea spray aerosols
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).ORCID iD: 0000-0001-6332-7658
2022 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The world’s oceans are the source of one of the most abundant types of natural aerosols, namely sea spray aerosols (SSA). By scattering solar radiation, SSA play a significant role in controlling the Earth’s radiation budget, while they are also involved in the formation of clouds, acting as cloud condensation nuclei (CCN). To understand the connection between biogeochemical processes occurring in the ocean and in the atmosphere, it is crucial to gain better insight into the detailed chemical composition of SSA, which broadly consists of sea salt and marine organic matter. The aim of this thesis is to (1) better understand the impact of ocean biological activity on the chemical composition of SSA and (2) improve the knowledge on the ability of SSA to transport different organic pollutants to the atmosphere. In Paper I it was shown that changes in the composition of marine organic matter during a phytoplankton bloom in the North Atlantic were clearly reflected in the composition of generated SSA. Increased chlorophyll a concentration in seawater was correlated with the presence of lipid-like compounds with high H/C and low O/C atomic ratios, and a consistent trend in chemical composition was observed for subsurface water, the surface microlayer, and generated SSA. Although the effect of biological processes on the composition of SSA organic matter was clear, in Paper II it was shown that during the phytoplankton bloom, the abundance of organic matter in SSA was fairly constant, without any significant influence on their CCN activity or the particle production flux. Paper III provided a mechanistic understanding of the enrichment of different cationic surfactants (CSs) in SSA through experiments conducted using a sea spray simulation chamber. It was shown that enrichment of the CSs was primarily driven by the alkyl chain length of the CSs but also affected by the different functional groups in the CSs. The highest enrichment of CSs on SSA was observed for quaternary amines followed by primary and tertiary amines. Interaction with dissolved humic acid was shown to decrease the enrichment of longer-chain amines while the enrichment was increased for shorter-chain ones. When the plunging jet flow rate was increased, enrichment in SSA was shown to increase, especially for lower water concentrations of surface-active compounds. The purpose of Paper IV was to improve the understanding of the enrichment behavior of perfluoroalkyl acids (PFAAs), which are strong anionic surfactants. Similar to CSs, it was shown that increasing the plunging jet flow increased the enrichment on SSA, from 43-88% for different PFAAs. The effect of different inorganic salts present in seawater on enrichment was also tested. Compared to chamber experiments prepared with ~35% NaCl water matrix, it was shown that the presence of other seawater ions, namely Ca2+ and Mg2+, increased the enrichment of some PFAAs, especially for those with longer perfluoroalkyl chains.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry, Stockholm University , 2022. , p. 43
Keywords [en]
Sea spray, Organic carbon, Dissolved organic matter, Phytoplankton bloom, Cationic surfactants, Perfluorinated alkyl acids, LC-MS, HRMS
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
URN: urn:nbn:se:su:diva-210894ISBN: 978-91-8014-096-6 (print)ISBN: 978-91-8014-097-3 (electronic)OAI: oai:DiVA.org:su-210894DiVA, id: diva2:1707789
Public defence
2022-12-16, Högbomsalen, Geovetenskapens hus, Svante Arrhenius väg 12, Stockholm, 10:00
Opponent
Supervisors
Available from: 2022-11-23 Created: 2022-11-01 Last updated: 2022-11-24Bibliographically approved
List of papers
1. Probing the impact of a phytoplankton bloom on the chemistry of nascent sea spray aerosol using high-resolution mass spectrometry
Open this publication in new window or tab >>Probing the impact of a phytoplankton bloom on the chemistry of nascent sea spray aerosol using high-resolution mass spectrometry
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2022 (English)In: Environmental Science: Atmospheres, E-ISSN 2634-3606, Vol. 2, no 5, p. 1152-1169Article in journal (Refereed) Published
Abstract [en]

Sea spray aerosol is the largest natural source of aerosol to Earth's atmosphere with significant impacts on climate. Despite this, estimates of the impact of sea spray aerosol on Earth's radiation budget are highly uncertain due to an overall lack of understanding of the physical and chemical factors controlling its composition. Critically, results from studies probing the importance of oceanic biological activity on the amount and type of organic matter present in nascent sea spray aerosol have been ambiguous. Some field studies have shown a relationship between the organic fraction of sea spray aerosol and oceanic primary productivity while others have reported no such relationships. Given this, we have probed the composition of seawater and nascent sea spray aerosol during a phytoplankton bloom in the North Atlantic using a novel liquid chromatography-mass spectrometry method. We observed that the composition of dissolved organic matter present in seawater changed as the phytoplankton bloom progressed over an 18 day period. Further, we observed changes to both the chemical composition of the organic matter present in seawater and the chemical composition of the organic matter present in the sea spray aerosol despite the organic matter mass fraction of the aerosol remaining unchanged. More specifically, we observed that the nascent sea spray aerosol became progressively more enriched in surface-active organic substances as the bloom progressed and that the sea spray aerosol had a distinct organic matter composition compared to the seawater. Thus, our work provides additional insight into the biological dependence of nascent sea spray aerosol composition.

National Category
Earth and Related Environmental Sciences
Identifiers
urn:nbn:se:su:diva-209446 (URN)10.1039/d2ea00028h (DOI)000841140100001 ()2-s2.0-85136522517 (Scopus ID)
Available from: 2022-09-19 Created: 2022-09-19 Last updated: 2025-02-07Bibliographically approved
2. Properties of sea spray aerosols during a spring phyto-plankton bloom on the Faroe Shelf in the North Atlantic
Open this publication in new window or tab >>Properties of sea spray aerosols during a spring phyto-plankton bloom on the Faroe Shelf in the North Atlantic
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(English)Manuscript (preprint) (Other academic)
National Category
Environmental Sciences
Research subject
Environmental Sciences
Identifiers
urn:nbn:se:su:diva-210910 (URN)
Available from: 2022-11-01 Created: 2022-11-01 Last updated: 2022-11-01
3. Enrichment behaviour of cationic surfactants on laboratory-generated sea spray aerosol
Open this publication in new window or tab >>Enrichment behaviour of cationic surfactants on laboratory-generated sea spray aerosol
2022 (English)Manuscript (preprint) (Other academic)
National Category
Analytical Chemistry Environmental Sciences
Research subject
Analytical Chemistry; Environmental Sciences
Identifiers
urn:nbn:se:su:diva-210892 (URN)
Available from: 2022-11-01 Created: 2022-11-01 Last updated: 2022-11-01
4. Influence of the composition of the inorganic salts in seawater and the plunging jet speed on the enrichment of perfluoroalkyl acids in laboratory-generated sea spray aerosol.
Open this publication in new window or tab >>Influence of the composition of the inorganic salts in seawater and the plunging jet speed on the enrichment of perfluoroalkyl acids in laboratory-generated sea spray aerosol.
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(English)Manuscript (preprint) (Other academic)
National Category
Environmental Sciences Analytical Chemistry
Research subject
Environmental Sciences; Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-210914 (URN)
Available from: 2022-11-01 Created: 2022-11-01 Last updated: 2022-11-01

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Radoman, Nikola

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