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Aerosol particles acting as cloud condensation nuclei (CCN) or ice nucleating particles (INP) play a major role in the formation and glaciation of clouds. Thereby they exert a strong impact on the radiation budget of the Earth. Data on abundance and properties of both types of particles are sparse, especially for remote areas of the world, such as the Southern Ocean (SO). In this work, we present unique results from ship-borne aerosol-particle-related in situ measurements and filter sampling in the SO region, carried out during the Antarctic Circumnavigation Expedition (ACE) in the Austral summer of 2016/17. An overview of CCN and INP concentrations on the Southern Ocean is provided and using additional quantities, insights regarding possible CCN and INP sources and origins are presented. CCN number concentrations spanned 2 orders of magnitude, e.g., for a supersaturation of 0.3 % values ranged roughly from 3 to 590 cm⁻³. CCN showed variable contributions of organic and inorganic material (inter-quartile range of hygroscopicity parameter κ from 0.2 to 0.9). No distinct size-dependence of κ was apparent, indicating homogeneous composition across sizes (critical dry diameter on average between 37 and 123 nm). The contribution of sea spray aerosol (SSA) to the CCN number concentration was on average small. Ambient INP number concentrations were measured in the temperature range from −5 to −27°C. Concentrations spanned up to 3 orders of magnitude, e.g., at −16°C from 0.2 to 100 m⁻³. Elevated values (above 10 m⁻³ at −16°C) were measured when the research vessel was in the vicinity of land, with lower and more constant concentrations when at sea. This hints towards terrestrial and/or coastal INP sources being dominant close to land. In pristine marine areas INP may originate from both oceanic sources and/or long range transport. Sampled aerosol particles (PM10) were analysed for sodium and methanesulfonic acid (MSA). Resulting mass concentrations were used as tracers for primary marine and secondary aerosol particles, respectively. Sodium, with an average concentration around 2.8 μg m⁻³, was found to dominate the sampled particle mass. MSA was highly variable over the SO, with concentrations up to 0.5 μg m⁻³ near the sea ice edge. A correlation analysis yielded strong correlations between sodium mass concentration and particle number concentration in the coarse mode, unsurprisingly indicating a significant contribution of SSA to that mode. CCN number concentration was highly correlated with the number concentration of Aitken and accumulation mode particles. This, together with a lack of correlation between sodium mass and Aitken and accumulation mode number concentrations, underlines the important contribution of non-SSA, probably secondarily formed particles, to the CCN population. INP number concentrations did not significantly correlate with any other measured aerosol physico-chemical parameter.

24 pages, 8 figures, supporting information https://doi.org/10.1029/2021JD034811.-- Data Availability Statement: The data set used in this study are available in (1) Antoine et al. (2019) available at https://doi.org/10.5281/zenodo.3406983; (2) Chen et al. (2019) available at https://doi.org/10.5281/zenodo.3559982; (3) Landwehr et al. (2020) available at https://doi.org/10.5281/zenodo.3836439; (4) Landwehr, Thurnherr et al. (2020) available at https://doi.org/10.5194/amt-13-3487-2020; (5) Schmale et al. (2019) available at https://doi.org/10.5281/zenodo.2636709; (6) Tatzelt et al. (2020) available at https://doi.org/10.5281/zenodo.3922147; (7) Thomalla et al., (2020) available at https://doi.org/10.5281/zenodo.3859515; (8) Thurnherr et al. (2020) available at https://doi.org/10.5281/zenodo.4031705; In addition, the fluorescent aerosol and gel–like POM measurements have been uploading as supplementary information supporting this article, In this study, we investigate the occurrence of primary biological aerosol particles (PBAP) over all sectors of the Southern Ocean (SO) based on a 90-day data set collected during the Antarctic Circumnavigation Expedition (ACE) in austral summer 2016–2017. Super-micrometer PBAP (1–16 µm diameter) were measured by a wide band integrated bioaerosol sensor (WIBS-4). Low (3σ) and high (9σ) fluorescence thresholds are used to obtain statistics on fluorescent and hyper-fluorescent PBAP, respectively. Our focus is on data obtained over the pristine ocean, that is, more than 200 km away from land. The results indicate that (hyper-)fluorescent PBAP are correlated to atmospheric variables associated with sea spray aerosol (SSA) particles (wind speed, total super-micrometer aerosol number concentration, chloride and sodium concentrations). This suggests that a main source of PBAP over the SO is SSA. The median percentage contribution of fluorescent and hyper-fluorescent PBAP to super-micrometer SSA was 1.6% and 0.13%, respectively. We demonstrate that the fraction of (hyper-)fluorescent PBAP to total super-micrometer particles positively correlates with concentrations of bacteria and several taxa of pythoplankton measured in seawater, indicating that marine biota concentrations modulate the PBAP source flux. We investigate the fluorescent properties of (hyper-)fluorescent PBAP for several events that occurred near land masses. We find that the fluorescence signal characteristics of particles near land is much more variable than over the pristine ocean. We conclude that the source and concentration of fluorescent PBAP over the open ocean is similar across all sampled sectors of the SO, The authors acknowledge funding for ACE-SPACE, ACE-SORPASSO by the Swiss Polar Institute, and Ferring Pharmaceuticals. ACE-SPACE was carried out with additional support from the European FP7 project BACCHUS (Grant Agreement 49603445). Gang Chen received funding from the cost action of Chemical On-Line cOmpoSition and Source Apportionment of fine aerosol (COLOSSAL, CA16109), a COST related project of the Swiss National Science Foundation, Source apportionment using long-term Aerosol Mass Spectrometry and Aethalometer Measurements (SAMSAM, IZCOZ0_177063). Sebastian Landwehr received funding from the Swiss Data Science Center project c17-02. Andrea Baccarin received funding from the Swiss National Science Foundation (Grant 200021_169090). Julia Schmale holds the Ingvar Kamprad Chair. Martin Gysel-Beer received funding from the ERC under Grant ERC-CoG-615922-BLACARAT. Charlotte Robinson received funding from the Australian Research Council (Grand ARC DP160103387), With the funding support of the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000928-S), of the Spanish Research Agency (AEI)

Aerosol characteristics over the Southern Ocean are surprisingly heterogeneous because of the distinct regional dynamics and marine microbial regimes. Satellite observations and model simulations underestimate the abundance of cloud condensation nuclei. Uncertainty in radiative forcing caused by aerosol-cloud interactions is about twice as large as for CO2 and remains the least well-understood anthropogenic contribution to climate change. A major cause of uncertainty is the poorly-quantified state of aerosols in the pristine-preindustrial atmosphere, which defines the baseline against which anthropogenic effects are calculated. The Southern Ocean is one of the few remaining near-pristine aerosol environments on Earth, but there are very few measurements to evaluate models. The Antarctic Circumnavigation Expedition: Study of Preindustrial-like Aerosols and their Climate Effects (ACE-SPACE) took place between December 2016 and March 2017 and covered the entire Southern Ocean region (Indian, Pacific and Atlantic Oceans, ship track > 33,000 km) including previously unexplored areas. In situ measurements covered aerosol characteristics (e.g., chemical composition, size distributions, and cloud condensation nuclei (CCN) number concentrations), trace gases and meteorological variables. Remote sensing observations of cloud properties, the physical and microbial ocean state, as well as back trajectory analyses are used to interpret the in situ data. The contribution of sea spray to CCN in the westerly wind belt can be larger than 50%. The abundance of methanesulfonic acid indicates local and regional microbial influence on CCN abundance in Antarctic coastal waters and in the open ocean. We use the in situ data to evaluate simulated CCN concentrations from a global aerosol model. The extensive, available ACE-SPACE dataset (https://zenodo.org/communities/spi-ace?page=1&size=20) provides an unprecedented opportunity to evaluate models and to reduce the uncertainty in radiative forcing associated with the natural processes of aerosol emission, formation, transport and processing occurring over the pristine Southern Ocean.

A data set of concurrent measurements of sea spray aerosol concentration, wind speed, sea state, and air and water temperature was acquired across all sectors of the S...

The aerosol-driven radiative effects on marine low-level cloud represent a large uncertainty in climate simulations, in particular over the Southern Ocean, which is also an important region for sea spray aerosol production. Observations of sea spray aerosol organic enrichment and the resulting impact on water uptake over the remote Southern Hemisphere are scarce, and therefore the region is under-represented in existing parameterisations. The Surface Ocean Aerosol Production (SOAP) voyage was a 23 d voyage which sampled three phytoplankton blooms in the highly productive water of the Chatham Rise, east of New Zealand. In this study we examined the enrichment of organics to nascent sea spray aerosol and the modifications to sea spray aerosol water uptake using in situ chamber measurements of seawater samples taken during the SOAP voyage. Primary marine organics contributed up to 23 % of the sea spray mass for particles with diameter less than approximately 1 µm and up to 79 % of the particle volume for 50 nm diameter sea spray. The composition of the submicron organic fraction was consistent throughout the voyage and was largely composed of a polysaccharide-like component, characterised by very low alkane-to-hydroxyl-concentration ratios of approximately 0.1–0.2. The enrichment of organics was compared to the output from the chlorophyll-a-based sea spray aerosol parameterisation suggested by Gantt et al. (2011) and the OCEANFILMS (Organic Compounds from Ecosystems to Aerosols: Natural Films and Interfaces via Langmuir Molecular Surfactants) models. OCEANFILMS improved on the representation of the organic fraction predicted using chlorophyll a, in particular when the co-adsorption of polysaccharides was included; however, the model still under-predicted the proportion of polysaccharides by an average of 33 %. Nascent 50 nm diameter sea spray aerosol hygroscopic growth factors measured at 90 % relative humidity averaged 1.93±0.08 and did not decrease with increasing sea spray aerosol organic fractions. The observed hygroscopicity was greater than expected from the assumption of full solubility, particularly during the most productive phytoplankton bloom (B1), during which organic fractions were greater than approximately 0.4. The water uptake behaviour observed in this study is consistent with that observed for other measurements of phytoplankton blooms and can be partially attributed to the presence of sea salt hydrates, which lowers the sea spray aerosol hygroscopicity when the organic enrichment is low. The inclusion of surface tension effects only marginally improved the modelled hygroscopicity, and a significant discrepancy between the observed and modelled hygroscopicity at high organic volume fractions remained. The findings from the SOAP voyage highlight the influence of biologically sourced organics on sea spray aerosol composition; these data improve the capacity to parameterise sea spray aerosol organic enrichment and water uptake.

Volatility-hygroscopicity tandem differential mobility analyzer measurements were used to infer the composition of sub-100 nm diameter Southern Ocean marine aerosols at Cape Grim in November and December 2007. This study focuses on a short-lived high sea spray aerosol (SSA) event on 7–8 December with two externally mixed modes in the Hygroscopic Growth Factor (HGF) distributions (90% relative humidity (RH)), one at HGF > 2 and another at HGF~1.5. The particles with HGF > 2 displayed a deliquescent transition at 73–75% RH and were nonvolatile up to 280°C, which identified them as SSA particles with a large inorganic sea-salt fraction. SSA HGFs were 3–13% below those for pure sea-salt particles, indicating an organic volume fraction (OVF) of up to 11–46%. Observed high inorganic fractions in sub-100 nm SSA is contrary to similar, earlier studies. HGFs increased with decreasing particle diameter over the range 16–97 nm, suggesting a decreased OVF, again contrary to earlier studies. SSA comprised up to 69% of the sub-100 nm particle number, corresponding to concentrations of 110–290 cm−3. Air mass back trajectories indicate that SSA particles were produced 1500 km, 20–40 h upwind of Cape Grim. Transmission electron microscopy (TEM) and X-ray spectrometry measurements of sub-100 nm aerosols collected from the same location, and at the same time, displayed a distinct lack of sea salt. Results herein highlight the potential for biases in TEM analysis of the chemical composition of marine aerosols.

The effect of soluble surfactant on the persistence of salt-water bubbles and their ability to produce aerosol particles upon bursting was investigated. Ensembles of individual, millimetric bubbles were produced in NaCl solutions of varying surfactant concentration. Aerosol production efficiency-a fundamental property of single bubbles defined as the number of particles produced per bubble film cap area-decreased by 79% to 98% following the addition of surfactant and increase in solution film pressure from 1-2 to 7-27 mN m(-1). The generated particle size distributions (0.01-10 mu m dry diameter) contained up to three modes and did not change much for film pressures up to 13.8 mN m(-1). The persistence of the bubbles at the water surface and the thickness of their film caps were investigated with high-speed videography. Addition of soluble surfactant increased average bubble persistence providing more time for the bubbles to drain and thin out with the aid of marginal regeneration flows. Bubble film cap thicknesses ranged from around 1 mu m for relatively clean, short-lived bubbles to less than 0.1 mu m for surfactant-stabilized, persistent bubbles. The suppression of aerosol production from the surfactant-stabilized bubbles may have resulted from the dramatic thinning of their caps or reduced surface forces at high film pressure. Previously reported Sea Spray Aerosol source functions were compared to measured aerosol production efficiencies and found to be significantly greater in magnitude, suggesting that there is a source of particles from whitecaps that was not captured in these single-bubble experiments.

Aerosol particles in the marine boundary layer include primary organic and salt particles from sea spray and combustion-derived particles from ships and coastal cities. These particle types serve as nuclei for marine cloud droplet activation, although the particles that activate depend on the particle size and composition as well as the supersaturation that results from cloud updraft velocities. The Eastern Pacific Emitted Aerosol Cloud Experiment (EPEACE) 2011 was a targeted aircraft campaign to assess how different particle types nucleate cloud droplets. As part of E-PEACE 2011, we studied the role of marine particles as cloud droplet nuclei and used emitted particle sources to separate particle-induced feedbacks from dynamical variability. The emitted particle sources included shipboard smoke-generated particles with 0.05-1 μm diameters (which produced tracks measured by satellite and had drop composition characteristic of organic smoke) and combustion particles from container ships with 0.05-0.2 μm diameters (which were measured in a variety of conditions with droplets containing both organic and sulfate components) [1]. Three central aspects of the collaborative E-PEACE results are: (1) the size and chemical composition of the emitted smoke particles compared to ship-track-forming cargo ship emissions as well as background marine particles, with particular attention to the role of organic particles, (2) the characteristics of cloud track formation for smoke and cargo ships, as well as the role of multi-layered low clouds, and (3) the implications of these findings for quantifying aerosol indirect effects. For comparison with the E-PEACE results, the preliminary results of the Stratocumulus Observations of Los-Angeles Emissions Derived Aerosol-Droplets (SOLEDAD) 2012 provided evidence of the cloud-nucleating roles of both marine organic particles and coastal urban pollution, with simultaneous measurements of the effective supersaturations of the clouds in the California coastal region.

The production, size, and chemical composition of sea spray aerosol (SSA) particles strongly depend on seawater chemistry, which is controlled by physical, chemical, and biological processes. Despite decades of studies in marine environments, a direct relationship has yet to be established between ocean biology and the physicochemical properties of SSA. The ability to establish such relationships is hindered by the fact that SSA measurements are typically dominated by overwhelming background aerosol concentrations even in remote marine environments. Herein, we describe a newly developed approach for reproducing the chemical complexity of SSA in a laboratory setting, comprising a unique ocean-atmosphere facility equipped with actual breaking waves. A mesocosm experiment was performed in natural seawater, using controlled phytoplankton and heterotrophic bacteria concentrations, which showed SSA size and chemical mixing state are acutely sensitive to the aerosol production mechanism, as well as to the type of biological species present. The largest reduction in the hygroscopicity of SSA occurred as heterotrophic bacteria concentrations increased, whereas phytoplankton and chlorophyll- a concentrations decreased, directly corresponding to a change in mixing state in the smallest (60–180 nm) size range. Using this newly developed approach to generate realistic SSA, systematic studies can now be performed to advance our fundamental understanding of the impact of ocean biology on SSA chemical mixing state, heterogeneous reactivity, and the resulting climate-relevant properties.

Sea spray production at the ocean surface is mediated by bubble bursting. A variety of means for producing bubbles in the laboratory have been developed to simulate the production of bubbles by breaking waves but none have made direct comparisons with actual breaking waves in natural seawater. This presentation will discuss the physical and chemical properties of aerosols generated by controlled breaking waves compared with the properties of those generated by a variety of bench-top methods that are more easily reproduced in a laboratory setting.