Sea Spray Aerosol (SSA) as a Source of Perfluoroalkyl Acids (PFAAs) to the Atmosphere: Field Evidence from Long-Term Air Monitoring

<div>Perfluoroalkyl acids (PFAAs) are persistent organic pollutants found throughout the world’s oceans. Previous research suggests that long-range atmospheric transport of these substances may be substantial. However, it remains unclear what the main sources of PFAAs to the atmosphere are. We have used a laboratory sea spray chamber to study water-to-air transfer of 11 PFAAs via sea spray aerosol (SSA). We observed significant enrichment of all PFAAs relative to sodium in the SSA generated. The highest enrichment was observed in aerosols with aerodynamic diameter < 1:6 µm, which had aerosol PFAA concentrations up to ~ 62000 times higher than the PFAA water concentrations in the chamber. In surface microlayer samples collected from the sea spray chamber, the enrichment of the substances investigated was orders of magnitude smaller than the enrichment observed in the aerosols. In experiments with mixtures of structural isomers, a lower contribution of branched PFAA isomers was observed in the SML in relation to the bulk water. However, no clear trend was observed for the comparison of structural isomers in SSA and bulk water. Using the measured enrichment factors of perfluoroctanoic acid and perfluorooctance sulfonic acid versus sodium we have estimated global annual emissions of these substances to the atmosphere via SSA as well as their global annual deposition to land areas. Our experiments suggest that SSA may currently be an important source of these substances to the atmosphere and, over certain areas where SSA deposition is important, a significant source to terrestrial environments.</div>

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Addendum to “Sea spray aerosol flux estimation based on long-term variation of wave statistics”: estimation based on long-term variation of wind statistics

Oceanologia ◽

10.1016/j.oceano.2015.11.003 ◽

2016 ◽

Vol 58 (2) ◽

pp. 150-153 ◽

Cited By ~ 1

Author(s):

Dag Myrhaug ◽

Hong Wang ◽

Lars Erik Holmedal

Keyword(s):

Sea Spray ◽

Wave Statistics ◽

Term Variation ◽

Sea Spray Aerosol ◽

Flux Estimation ◽

Wind Statistics

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Global Transport of Perfluoroalkyl Acids via Sea Spray Aerosol

10.26434/chemrxiv.7326716 ◽

2018 ◽

Author(s):

Jana Johansson ◽

Matthew Salter ◽

Juan Acosta Navarro ◽

Caroline Leck ◽

E. Douglas Nilsson ◽

...

Keyword(s):

Atmospheric Transport ◽

Enrichment Factors ◽

Bulk Water ◽

Perfluoroalkyl Acids ◽

Sea Spray ◽

Surface Microlayer ◽

Spray Chamber ◽

Structural Isomers ◽

Clear Trend ◽

Sea Spray Aerosol

<div>Perfluoroalkyl acids (PFAAs) are persistent organic pollutants found throughout the world’s oceans. Previous research suggests that long-range atmospheric transport of these substances may be substantial. However, it remains unclear what the main sources of PFAAs to the atmosphere are. We have used a laboratory sea spray chamber to study water-to-air transfer of 11 PFAAs via sea spray aerosol (SSA). We observed significant enrichment of all PFAAs relative to sodium in the SSA generated. The highest enrichment was observed in aerosols with aerodynamic diameter < 1:6 µm, which had aerosol PFAA concentrations up to ~ 62000 times higher than the PFAA water concentrations in the chamber. In surface microlayer samples collected from the sea spray chamber, the enrichment of the substances investigated was orders of magnitude smaller than the enrichment observed in the aerosols. In experiments with mixtures of structural isomers, a lower contribution of branched PFAA isomers was observed in the SML in relation to the bulk water. However, no clear trend was observed for the comparison of structural isomers in SSA and bulk water. Using the measured enrichment factors of perfluoroctanoic acid and perfluorooctance sulfonic acid versus sodium we have estimated global annual emissions of these substances to the atmosphere via SSA as well as their global annual deposition to land areas. Our experiments suggest that SSA may currently be an important source of these substances to the atmosphere and, over certain areas where SSA deposition is important, a significant source to terrestrial environments.</div>

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Sea spray aerosol flux estimation based on long-term variation of wave statistics

Oceanologia ◽

10.1016/j.oceano.2015.04.001 ◽

2015 ◽

Vol 57 (3) ◽

pp. 288-292 ◽

Cited By ~ 1

Author(s):

Dag Myrhaug ◽

Hong Wang ◽

Lars Erik Holmedal

Keyword(s):

Sea Spray ◽

Wave Statistics ◽

Term Variation ◽

Sea Spray Aerosol ◽

Flux Estimation

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Sea Spray Aerosol Chamber Study on Selective Transfer and Enrichment of Free and Combined Amino Acids

ACS Earth and Space Chemistry ◽

10.1021/acsearthspacechem.1c00080 ◽

2021 ◽

Author(s):

Nadja Triesch ◽

Manuela van Pinxteren ◽

Matthew Salter ◽

Christian Stolle ◽

Ryan Pereira ◽

...

Keyword(s):

Amino Acids ◽

Sea Spray ◽

Selective Transfer ◽

Chamber Study ◽

Sea Spray Aerosol ◽

Aerosol Chamber

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Linking variations in sea spray aerosol particle hygroscopicity to composition during two microcosm experiments

10.5194/acp-2016-36 ◽

2016 ◽

Author(s):

Sara D. Forestieri ◽

Gavin C. Cornwell ◽

Taylor M. Helgestad ◽

Kathryn A. Moore ◽

Christopher Lee ◽

...

Keyword(s):

Light Scattering ◽

Relative Humidity ◽

Salt Content ◽

Sea Salt ◽

Sea Spray ◽

Hygroscopic Growth ◽

Phytoplankton Blooms ◽

Aerosol Composition ◽

Sea Spray Aerosol ◽

Indoor And Outdoor

Abstract. The extent to which water uptake influences the light scattering ability of marine sea spray aerosol (SSA) particles depends critically on SSA chemical composition. The organic fraction of SSA can increase during phytoplankton blooms, decreasing the salt content and therefore the hygroscopicity of the particles. In this study, subsaturated hygroscopic growth factors at 85 % relative humidity (GF(85 %)) of SSA particles were quantified during two induced phytoplankton blooms in marine aerosol reference tanks (MARTs). One MART was illuminated with fluorescent lights and the other was illuminated with sunlight, referred to as the "indoor" and "outdoor" MARTs, respectively. GF(85 %) values for SSA particles were derived from measurements of light scattering and particle size distributions, concurrently with online single particle and bulk aerosol composition measurements. During both microcosm experiments, the observed bulk average GF(85 %) values were depressed substantially relative to pure, inorganic sea salt, by 10 to 19 %, with a one (indoor MART) and six (outdoor MART) day lag between GF(85 %) depression and the peak chlorophyll-a concentrations. The fraction of organiccontaining SSA particles generally increased after the peak of the phytoplankton blooms. The GF(85 %) values were inversely correlated with the fraction of particles containing organic or other biological markers. This indicates these particles were less hygroscopic than the particles identified as predominately sea salt containing and demonstrates a clear relationship between SSA particle composition and the sensitivity of light scattering to variations in relative humidity. The implications of these observations to the direct climate effects of SSA particles are discussed.

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Gaseous chemistry and aerosol mechanism developments for version 3.5.1 of the online regional model, WRF-Chem

Geoscientific Model Development ◽

10.5194/gmd-7-2557-2014 ◽

2014 ◽

Vol 7 (6) ◽

pp. 2557-2579 ◽

Cited By ~ 30

Author(s):

S. Archer-Nicholls ◽

D. Lowe ◽

S. Utembe ◽

J. Allan ◽

R. A. Zaveri ◽

...

Keyword(s):

Gas Phase ◽

Chemical Mechanism ◽

Reduced Form ◽

Sea Spray ◽

Wind Fields ◽

Aerosol Composition ◽

Aerosol Emission ◽

Sea Spray Aerosol ◽

The Impact ◽

Phase Chemical

Abstract. We have made a number of developments to the Weather, Research and Forecasting model coupled with Chemistry (WRF-Chem), with the aim of improving model prediction of trace atmospheric gas-phase chemical and aerosol composition, and of interactions between air quality and weather. A reduced form of the Common Reactive Intermediates gas-phase chemical mechanism (CRIv2-R5) has been added, using the Kinetic Pre-Processor (KPP) interface, to enable more explicit simulation of VOC degradation. N2O5 heterogeneous chemistry has been added to the existing sectional MOSAIC aerosol module, and coupled to both the CRIv2-R5 and existing CBM-Z gas-phase schemes. Modifications have also been made to the sea-spray aerosol emission representation, allowing the inclusion of primary organic material in sea-spray aerosol. We have worked on the European domain, with a particular focus on making the model suitable for the study of nighttime chemistry and oxidation by the nitrate radical in the UK atmosphere. Driven by appropriate emissions, wind fields and chemical boundary conditions, implementation of the different developments are illustrated, using a modified version of WRF-Chem 3.4.1, in order to demonstrate the impact that these changes have in the Northwest European domain. These developments are publicly available in WRF-Chem from version 3.5.1 onwards.

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