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Understanding ocean-cloud interactions and their effect on climate requires that atmospheric new particle formation is characterized. Yet, the process of particle formation from marine biogenic gaz-phase emissions has not been evidenced in the open ocean lower atmosphere, partly due to the naturally low concentrations of these particles in remote oceanic places. Here we show, using new ship-borne air-sea interface enclosures, that new particles are formed in relation to marine micro-biology present in the seawater. The chemical analysis of newly formed clusters with API-ToF-MS shows unexpected results, implicating nucleating coumpounds and pathways that are usually not taken into account in nucleation processes.

Air-sea fluxes of dimethyl sulphide (DMS) and methanethiol (MeSH) from surface seawater in the remote Southern Pacific Ocean were measured in three Air-Sea Interface Tank (ASIT) experiments during the Sea2Cloud voyage in March 2020. The measured fluxes of 0.78 ± 0.44 ng m-2 s-1 and 0.05 ± 0.03 ng m-2 s-1 for DMS and MeSH, respectively, varied between experiments reflecting the different water mass types investigated, with lowest fluxes with subtropical water and highest with biologically-active water with sub-Tropical water and highest from the sub-Tropical Front. Measured DMS fluxes were consistent with calculated fluxes from a two-layer model using DMS concentration in the ASIT seawater. The experiments also determined the influence of elevated ozone, with one ASIT headspace amended with 10 ppbv ozone while the other provided an unamended control. Elevated ozone resulted in a decrease in DMS flux, corresponding to decreased conversion of dimethylsulfoniopropionate (DMSP) to DMS in the seawater. The MeSH:DMS flux range was 11–18 % across experiments, in line with previous observations, indicating that MeSH represents a significant contribution to the atmospheric sulfur budget. Using the ASIT results in combination with ambient seawater concentrations during Sea2Cloud, significant linear correlations were identified for both DMS and MeSH fluxes with nanophytoplankton cell abundance (rDMS= 0.73 and rMeSH= 0.86), indicating an important role for this phytoplankton size class, and also its potential as a proxy for estimating DMS and MeSH emissions in chemistry-climate models.

Benzene, toluene, ethylbenzene and xylenes can contribute to hydroxyl reactivity and secondary aerosol formation in the atmosphere. These aromatic hydrocarbons are typically classified as anthropogenic air pollutants, but there is growing evidence of biogenic sources, such as emissions from plants and phytoplankton. Here we use a series of shipborne measurements of the remote marine atmosphere, seawater mesocosm incubation experiments and phytoplankton laboratory cultures to investigate potential marine biogenic sources of these compounds in the oceanic atmosphere. Laboratory culture experiments confirmed marine phytoplankton are a source of benzene, toluene, ethylbenzene, xylenes and in mesocosm experiments their sea-air fluxes varied between seawater samples containing differing phytoplankton communities. These fluxes were of a similar magnitude or greater than the fluxes of dimethyl sulfide, which is considered to be the key reactive organic species in the marine atmosphere. Benzene, toluene, ethylbenzene, xylenes fluxes were observed to increase under elevated headspace ozone concentration in the mesocosm incubation experiments, indicating that phytoplankton produce these compounds in response to oxidative stress. Our findings suggest that biogenic sources of these gases may be sufficiently strong to influence atmospheric chemistry in some remote ocean regions. A group of aromatic hydrocarbons in the remote marine atmosphere, typically classified as anthropogenic pollutants, are attributable to local biogenic sources, according to shipborne observations and mesocosm experiments.

We present here the results obtained during an intensive field campaign conducted in the framework of the French “BIO-MAÏDO” (Bio-physico-chemistry of tropical clouds at Maïdo (Réunion Island): processes and impacts on secondary organic aerosols’ formation) project. This study integrates an exhaustive chemical and microphysical characterization of cloud water obtained in March–April 2019 at Reunion Island (Indian Ocean). Fourteen cloud samples have been collected along the slope of this mountainous island. A comprehensive chemical characterization of these samples is performed, including inorganic ions, metals, oxidants, and organic matter (organic acids, sugars, amino acids, carbonyls, and low-soluble volatile organic compounds (VOCs)). Cloud water presents high molecular complexity with elevated water-soluble organic matter content partly modulated by microphysical cloud properties. As expected, our findings show the presence of compounds of marine origin in cloud water samples (e.g., chloride, sodium) demonstrating ocean–cloud exchanges. However, the non-sea salt fraction of sulphate varies between 38 and 91 %, indicating the presence of other sources. Also, the presence of amino acids and for the first time in cloud waters of sugars, clearly indicates that biological activities contribute to the cloud water chemical composition. A significant variability between events is observed in the dissolved organic content (25.5 ± 18.4 mgC L−1), with levels reaching up to 62 mgC L−1. This variability was not similar for all the measured compounds, suggesting the presence of dissimilar emission sources or production mechanisms. For that, a statistical analysis is performed based on back-trajectory calculations using the CAT (Computing Atmospheric Trajectory Tool) model associated with land cover registry. These investigations reveal that air mass origins and microphysical variables do not fully explain the variability observed in cloud chemical composition, highlighting the complexity of emission sources, multiphasic transfer, and chemical processing in clouds. Additionally, several VOCs (oxygenated and low-soluble VOCs) were analysed in both gas and aqueous phases. Significant levels of biogenic low-soluble VOCs were detected in the aqueous phase, indicating the cloud-terrestrial vegetation exchange. Cloud scavenging of VOCs is assessed and compared to Henry’s law equilibrium to evaluate potential super or sub saturation conditions. The evaluation reveals the supersaturation of low-soluble VOCs from both natural and anthropogenic sources. Our results depict even higher supersaturation of terpenoids, suggesting their importance in the aqueous phase chemistry in highly impacted tropical areas.

Even though oceans cover over 70% of the Earth’s surface, the ways in which oceans interact with climate are not fully known. Marine micro-organisms such as phytoplankton can play an important role in regulating climate by releasing different chemical species into air. In air these chemical species can react and form new aerosol particles. If grown to large enough sizes, aerosols can influence climate by acting as cloud condensation nuclei which influence the formation and properties of clouds. Even though a connection of marine biology and climate through aerosol formation was first proposed already over 30 years ago, the processes related to this connection are still uncertain.To unravel how seawater properties affect aerosol formation and to identify which chemical species are responsible for aerosol formation, we built two Air-Sea-Interaction Tanks (ASIT) that isolate 1000 l of seawater and 1000 l of air directly above the water. The used seawater was collected from different locations during a ship campaign on board the R/V Tangaroa in the South West Pacific Ocean, close to Chatham Rise, east of New Zealand. Seawater from one location was kept in the tanks for 2-3 days and then changed. By using seawater collected from different locations, we could obtain water with different biological populations. To monitor the seawater, we took daily samples to determine its chemical and biological properties.The air in the tanks was continuously flushed with particle filtered air. This way the air had on average 40 min to interact with the seawater surface before being sampled. Our air sampling was continuous and consisted of aerosol and air chemistry measurements. The instrumentation included measurements of aerosol number concentration from 1 to 500 nm and chemical species ranging from ozone and sulphur dioxide to volatile organic compounds and chemical composition of molecular clusters.Joining the seawater and atmospheric data together can give us an idea of what chemical species are emitted from the water into the atmosphere and whether these species can form new aerosol particles. Our preliminary results show a small number of particles in the freshly nucleated size range of 1-3 nm in the ASIT headspaces, indicating that new aerosol particles can form in the ASIT headspaces. In this presentation, we will also explore which chemical species could be responsible for aerosol formation and which plankton groups could be related to the emissions of these species. Combining these results with ambient data and modelling work can shed light on how important new particle formation from marine sources is for climate.Acknowledgements: Sea2Cloud project is funded by European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (Grant agreement No. 771369).

The puy de Dôme (pdD) altitude research station is located in the centre of France (45° 46' N, 2° 57' E, 1465 m altitude a.s.l), 16 km from the town of Clermont-Ferrand. This station is a global GAW station (PUY), and is part of the ACTRIS-2 integrating activities (H2020). Long series of meteorological parameters such as wind speed and direction, temperature, pressure, relative humidity and radiation, atmospheric trace gases (O3, NOx, SO2, CO2, CO), and physical, optical and chemical properties of aerosols (particle size, black carbon, mass,..) are available.Cartridge sampling measurements are performed to link the observations of volatile organic compounds (VOCs) within ACTRIS and GAW. A selection of VOCs, including a large set of non-methane hydrocarbons and some terpenes (isoprene, α-pinene), was measured during summer 2010, spring and summer 2011, winter 2012, summer and winter 2013, summer 2015, and twice a week in 2017, 2018 and 2019. The analysis of VOCs collected off-line on Tenax/Carbosieve III or Tenax TA cartridges was carried out using gas chromatography coupled with thermo-desorption with mass spectrometry (GC-MS).In August 2018, a new gas chromatography (GC-FID) system was installed at the station. It allows the acquisition of non-methane hydrocarbons (C5-C10) with a temporal resolution of two hours.The reactive gas measurement series are analysed in terms of observed levels (i), diurnal and seasonal variability (ii), air mass origins (iii) and sources of these gaseous pollutants (iv).(i) The level observed at the PUY station is discussed and compared with two other stations: Monte Cimone (mainly in the free troposphere) and Hohenpeissenberg (mainly in the planetary boundary layer PBL).(ii) As the height of the PBL changes with a diurnal cycle and with the seasons, the PUY station is in the different layers of the troposphere during the year impacting the measured concentrations.(iii) In order to determine the transport pathways of the air masses before their arrival at the pdD site, the HYSPLIT (Hybrid Single Particle Lagrangian Trajectory) model was used. Trajectories were classified according to their predominant transport direction prior to measurement, either continental (C), marine (M), modified marine (Mod), Mediterranean (Med), or mixed according to their trajectories. In order to determine the influence of wind direction, the pollution wind rose was determined for the main pollutants.(iv) Comparison with temperature, air mass origins, boundary layer height are used to identify the main parameters influencing the variability of VOCs. The Principal Component Analysis (PCA) has been performed to deduce correlations between the main atmospheric species and their main determinants.

For the last twenty-five years, CO-PDD (Cézeaux-Aulnat-Opme-puy de Dôme) has evolved to become a full instrumented platform for atmospheric research. It is nationally accredited by CNRS, the French national center for scientific research, and recognized as a global station in the GAW network (Global Atmospheric Watch). It is a reference site of the European and national research infrastructures ACTRIS (Aerosol Cloud and Trace gases Research Infrastructure) and ICOS (Integrated Carbon Observing System). The site located on-top of the puy de Dôme mountain (1465 m a.s.l.) is completed by additional sites located at lower altitudes and adding the vertical dimension to the atmospheric observations: Opme (660 m a.s.l.), Cézeaux (410 m) and Aulnat (330 m). On the sites has been developed a unique combination of in-situ and remote sensing measurements capturing and documenting the variability of particulate and gaseous atmospheric composition, but also the optical, biochemical and physical properties of aerosol particles, clouds and precipitations. Given its location far away from any major emission sources, its altitude and the mountain orography, the puy de Dôme station is ideally situated to sample different air masses in the boundary layer or in the free troposphere depending on time of day and seasons. It is also an ideal place to study cloud properties with frequent presence of clouds at the top in autumn and winter. As a result of the natural conditions prevailing at the site and of the very exhaustive instrumental deployment, scientific studies at puy de Dôme strongly contribute to improving the knowledge in atmospheric sciences including the characterization of trends and variability, the understanding of complex and interconnected processes (microphysical, chemical, biological, chemical and dynamical) and providing a reference point for climate models. In this context, CO-PDD is a pilot site to conduct instrumental development inside its wind tunnel for testing liquid/ice cloud probes in natural conditions, or in-situ systems to collect aerosol and cloud. This paper reviews 25 years (1995–2020) of atmospheric observation at the station, and related scientific research contributing to atmospheric and climate science.