Can sea spray aerosol be a source of gas-phase perfluoroalkyl substances (PFAS)? A study in the Eastern North Atlantic Ocean

Sea spray aerosol (SSA) formed after wave breaking at the ocean surface influences our climate by scattering incoming solar radiation and acting as cloud condensation nuclei. Furthermore, they provide a microenvironment for aqueous phase chemistry, selective uptake of surfactants, and gas-to-particle partitioning of compounds by providing an acidic pH at the air-water interface (Angle et al., 2022). Despite these known effects, a crucial question remains unanswered: which volatile organic compounds (VOCs) are emitted from SSA, and how do they change over time via atmospheric aging? To address this, we designed a novel experimental setup during the AGENA* Campaign 2022 at Graciosa Island, Portugal. For the first time, we connected a sea spray simulation chamber to a chemical ionization mass spectrometer (CIMS) to measure the freshly emitted gases from both seawater and SSA. Additionally, we aged the samples for an equivalent period of about 3-3.5 days in an oxidation flow reactor to investigate compositional changes after ageing. Surprisingly, our findings reveal that nearly half of the mass-spectrometer signal from the fresh samples constituted fluorinated compounds, specifically short-chain perfluoroalkyl carboxylic acids - a class of perfluoroalkyl substances (PFAS). While, previous studies have shown that SSA can release and play a key role in the long-range transport of PFAS, these studies have primarily focused on particle-phase emissions (Johansson et al., 2019, Sha et al, et al., 2022). In contrast, our study provides new insights into oceanic PFAS emissions and transport to the atmosphere by examining gas-phase emissions.   Furthermore, we observed that the gas-phase PFAS almost completely disappears after ageing. Our hypothesis is that these compounds partition into the particle phase. We plan to test this hypothesis by analyzing the particle filters collected during the campaign. *Aerosol Growth in the Eastern North Atlantic (AGENA) https://www.arm.gov/research/campaigns/ena2022agena Angle, K. J., Crocker, D. R., Simpson, R. M., Mayer, K. J., Garofalo, L. A., Moore, A. N., ... & Grassian, V. H. (2021). Acidity across the interface from the ocean surface to sea spray aerosol. Proceedings of the National Academy of Sciences, 118(2), e2018397118. Johansson, J. H., Salter, M. E., Navarro, J. A., Leck, C., Nilsson, E. D., & Cousins, I. T. (2019). Global transport of perfluoroalkyl acids via sea spray aerosol. Environmental Science: Processes & Impacts, 21(4), 635-649. Sha, B., Johansson, J. H., Tunved, P., Bohlin-Nizzetto, P., Cousins, I. T., & Salter, M. E. (2021). Sea spray aerosol (SSA) as a source of perfluoroalkyl acids (PFAAs) to the atmosphere: field evidence from long-term air monitoring. Environmental Science & Technology, 56(1), 228-238.