Sea Spray Aerosol Particles Research Articles

Underestimated role of sea surface temperature in sea spray aerosol formation and climate effects

The uncertainty regarding the correlation between sea spray aerosol (SSA) formation and sea surface temperature (SST) hinders the accurate estimation of SSA’s impact on global climate. Here, we developed a temperature-controlled plunging SSA simulation tank to investigate the impact of SST on SSA formation from two perspectives: SSA particle size distribution and organic enrichment. Our findings show that SSA particle size decreases with decreasing SST, as exhibited by an increase in SSA within Aitken mode and a decrease in SSA within accumulation and coarse modes. SST can significantly enhance organic enrichment in SSA particles, while the multiplicative increases vary from 2 to 10 times depending on the organic matter species and the SSA particle size. Based on our experimental results, it is predicted that SST reduction may lead to a significantly higher contribution of Aitken modal SSA-derived CCN in cold waters (0 °C) than in warm waters (30 °C). Additionally, we incorporate SST for the first time in estimating the global flux of dissolved organic carbon (DOC) emitted via SSA, yielding a value ranging from 23.45 to 55.78 Tg C yr−1. Compared to previous works, our study reveals the crucial role of SST in influencing both cloud formation and the atmospheric organic burden of SSA.

Sea spray emissions from the Baltic Sea: comparison of aerosol eddy covariance fluxes and chamber-simulated sea spray emissions

Abstract. To compare in situ and laboratory estimates of sea spray aerosol (SSA) production fluxes, we conducted two research campaigns in the vicinity of an eddy covariance (EC) flux tower on the island of Östergarnsholm in the Baltic Sea during May and August 2021. To accomplish this, we performed EC flux measurements for particles with diameters between 0.25 and 2.5 µm simultaneously with laboratory measurements using a plunging jet sea spray simulation chamber containing local seawater sampled close to the footprint of the flux tower. We observed a log-linear relationship between wind speed and EC-derived SSA emission fluxes, a power-law relationship between significant wave height and EC-derived SSA emission fluxes, and a linear relationship between wave Reynolds number and EC-derived SSA emission fluxes, all of which are consistent with earlier studies. Although we observed a weak negative relationship between particle production in the sea spray simulation chamber and seawater chlorophyll-α concentration and a weak positive relationship with the concentration of fluorescent dissolved organic matter in seawater, we did not observe any significant impact of dissolved oxygen on particle production in the chamber. To obtain an estimate of the size-resolved emission spectrum for particles with dry diameters between 0.015 and 10 µm, we combined the estimates of SSA particle production fluxes obtained using the EC measurements and the chamber measurements in three different ways: (1) using the traditional continuous whitecap method, (2) using air entrainment measurements, and (3) simply scaling the chamber data to the EC fluxes. In doing so, we observed that the magnitude of the EC-derived emission fluxes compared relatively well to the magnitude of the fluxes obtained using the chamber air entrainment method as well as the previous flux measurements of Nilsson et al. (2021) and the parameterizations of Mårtensson et al. (2003) and Salter et al. (2015). As a result of these measurements, we have derived a wind-speed-dependent and wave-state-dependent SSA parameterization for particles with dry diameters between 0.015 and 10 µm for low-salinity waters such as the Baltic Sea, thus providing a more accurate estimation of SSA production fluxes.

Aircraft ice-nucleating particle and aerosol composition measurements in the western North American Arctic

Abstract. Knowledge of the temperature-dependent concentration of ice-nucleating particles (INPs) is crucial to understanding the properties of mixed-phase clouds. However, the sources, transport and removal of INPs around the globe, and particularly in the Arctic region, are poorly understood. In the Arctic winter and spring, when many local sources are covered by ice and snow, it is not clear which INP types are important. In this study, we present a new dataset of aircraft-based immersion mode INP measurements and aerosol size-resolved composition in the western North American Arctic from 11 to 21 March 2018. Aerosol samples were collected between ∼ 70 and 600 m above the surface on filters that were analysed using both a freezing droplet-based assay and scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS). The measured INP concentrations were at or close to the limit of detection, with concentrations at −20 ∘C of 1 L−1 or below. The size-resolved composition measurements indicates that the aerosol concentrations were low, dominated mostly by sea spray aerosol and mineral dust. Further analysis shows that mineral dust is important for the ice-nucleating properties of our samples, dominating over the sea spray aerosol particles in the four cases we analysed, suggesting that mineral dust is a relevant type of INP in the Alaskan springtime Arctic. Furthermore, the INP concentrations are more consistent with fertile soil dusts that have an ice-active biological component than what would be expected for the ice-active mineral K-feldspar alone. While we cannot rule out local high-latitude sources of dust, the relatively small size of the mineral dust implies that the dust was from distant sources.

Revealing the Impacts of Chemical Complexity on Submicrometer Sea Spray Aerosol Morphology.

Sea spray aerosol (SSA) ejected through bursting bubbles at the ocean surface is a complex mixture of salts and organic species. Submicrometer SSA particles have long atmospheric lifetimes and play a critical role in the climate system. Composition impacts their ability to form marine clouds, yet their cloud-forming potential is difficult to study due to their small size. Here, we use large-scale molecular dynamics (MD) simulations as a "computational microscope" to provide never-before-seen views of 40 nm model aerosol particles and their molecular morphologies. We investigate how increasing chemical complexity impacts the distribution of organic material throughout individual particles for a range of organic constituents with varying chemical properties. Our simulations show that common organic marine surfactants readily partition between both the surface and interior of the aerosol, indicating that nascent SSA may be more heterogeneous than traditional morphological models suggest. We support our computational observations of SSA surface heterogeneity with Brewster angle microscopy on model interfaces. These observations indicate that increased chemical complexity in submicrometer SSA leads to a reduced surface coverage by marine organics, which may facilitate water uptake in the atmosphere. Our work thus establishes large-scale MD simulations as a novel technique for interrogating aerosols at the single-particle level.

Ocean-atmosphere interactions: Different organic components across Pacific and Southern Oceans

Sea spray aerosol (SSA) particles strongly influence clouds and climate but the potential impact of ocean microbiota on SSA fluxes is still a matter of active research. Here–by means of in situ ship-borne measurements–we explore simultaneously molecular-level chemical properties of organic matter (OM) in oceans, sea ice, and the ambient PM2.5 aerosols along a transect of 15,000 km from the western Pacific Ocean (36°13′N) to the Southern Ocean (75°15′S). By means of orbitrap mass spectrometry and optical characteristics, lignin-like material (24 ± 5 %) and humic material (57 ± 8 %) were found to dominate the pelagic Pacific Ocean surface, while intermediate conditions were observed in the Pacific-Southern Ocean waters. In the marine atmosphere, we found a gradient of features in the aerosol: lignin-like material (31 ± 9 %) dominating coastal areas and the pelagic Pacific Ocean, whereas lipid-like (23 ± 16 %) and protein-like (11 ± 10 %) OM controlled the sympagic Southern Ocean (sea ice-influence). The results of this study showed that the OM composition in the ocean, which changes with latitude, affects the OM in aerosol compositions in the atmosphere. This study highlights the importance of the global-scale OM monitoring of the close interaction between the ocean, sea ice, and the atmosphere. Sympagic primary marine aerosols in polar regions must be treated differently from other pelagic-type oceans.

Insoluble lipid film mediates transfer of soluble saccharides from the sea to the atmosphere: the role of hydrogen bonding

Abstract. Saccharides are a large portion of organic matter in sea spray aerosol (SSA). Although they can affect climate-related properties of SSA, the mechanism through which saccharides are transferred from bulk seawater to the ocean surface and ultimately into SSA is still debated. Here, the transfer of small soluble saccharides was validated using a controlled plunging jet sea spray aerosol generator to better understand the wide range of particle properties produced by natural seawater mixed with model organic species, glucose and trehalose. We showed that both soluble saccharides can promote the production of SSA particles, and the presence of trehalose could increase the SSA number concentration by 49.4 %. Conversely, the role of the insoluble fatty acid film on the seawater surface greatly reduced the production of SSA. The resulting inorganic–organic mixed particles identified by the transmission electron microscope (TEM) showed typical core–shell morphology. A Langmuir model was used to parameterize the adsorption and distribution of saccharide into SSA across the bubble surface, while infrared reflection–absorption spectroscopy (IRRAS) combined with Langmuir isotherms was undertaken to examine the effects of aqueous subphase soluble saccharides with various concentrations on the phase behavior, structure, and ordering of insoluble lipid monolayers adsorbed at the air/water interface. We found that the adsorption of glucose and trehalose on the fatty acid monolayer led to the expansion of the mean molecular area. Saccharide–lipid interactions increased with increasing complexity of the saccharide in the order of glucose < trehalose. In a seawater solution, the effects of dissolved saccharides on the ordering and organization of fatty acid chains were muted. The enhancement of the carbonyl band to the low wavenumber region implied that soluble saccharides can form new hydrogen bonds with fatty acid molecules by displacing large amounts of water near the polar headgroups of fatty acids. Our results indicate that the interaction between soluble saccharides and insoluble fatty acid molecules through hydrogen bonds is an important component of the sea–air transfer mechanism of saccharides.

PFAS on atmospheric aerosol particles: a review.

Per- and polyfluoroalkyl substances (PFAS) are persistent organic pollutants of concern to human health. These synthetic chemicals are in widespread use for consumer products, firefighting foams, and industrial applications. They have been detected all over the globe, including at remote locations distant from any possible point sources. One mechanism for long-range transport of PFAS is through sorption to aerosol particles in the atmosphere. PFAS can be transferred from the sea surface to sea spray aerosol particles through wave breaking and bubble bursting, and PFAS emitted to the atmosphere in the gas phase can sorb to particulate matter through gas-particle partitioning. Here we present a comprehensive review of global measurements of PFAS on ambient particulate matter dating back to the first reports from the early 2000s. We summarize findings for the historically important C8 species, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), including detection of isomers and size-segregated measurements, as well as studies of newer and emerging PFAS. We conclude that long-term monitoring of PFAS on particulate matter should be expanded to include more measurement sites in under-sampled regions of the world and that further non-targeted work to identify novel PFAS structures is needed as PFAS manufacturing and regulations continue to evolve.

In situ particle sampling relationships to surface and turbulent fluxes using large eddy simulations with Lagrangian particles

Abstract. Source functions for mechanically driven coarse-mode sea spray and dust aerosol particles span orders of magnitude owing to a combination of physical sensitivity in the system and large measurement uncertainty. Outside special idealized settings (such as wind tunnels), aerosol particle fluxes are largely inferred from a host of methods, including local eddy correlation, gradient methods, and dry deposition methods. In all of these methods, it is difficult to relate point measurements from towers, ships, or aircraft to a general representative flux of aerosol particles. This difficulty is from the particles' inhomogeneous distribution due to multiple spatiotemporal scales of an evolving marine environment. We hypothesize that the current representation of a point in situ measurement of sea spray or dust particles is a likely contributor to the unrealistic range of flux and concentration outcomes in the literature. This paper aims to help the interpretation of field data: we conduct a series of high-resolution, cloud-free large eddy simulations (LESs) with Lagrangian particles to better understand the temporal evolution and volumetric variability of coarse- to giant-mode marine aerosol particles and their relationship to turbulent transport. The study begins by describing the Lagrangian LES model framework and simulates flux measurements that were made using numerical analogs to field practices such as the eddy covariance method. Using these methods, turbulent flux sampling is quantified based on key features such as coherent structures within the marine atmospheric boundary layer (MABL) and aerosol particle size. We show that for an unstable atmospheric stability, the MABL exhibits large coherent eddy structures, and as a consequence, the flux measurement outcome becomes strongly tied to spatial length scales and relative sampling of crosswise and streamwise sampling. For example, through the use of ogive curves, a given sampling duration of a fixed numerical sampling instrument is found to capture 80 % of the aerosol flux given a sampling rate of zf/w∗∼ 0.2, whereas a spanwise moving instrument results in a 95 % capture. These coherent structures and other canonical features contribute to the lack of convergence to the true aerosol vertical flux at any height. As expected, sampling all of the flow features results in a statistically robust flux signal. Analysis of a neutral boundary layer configuration results in a lower predictive range due to weak or no vertical roll structures compared to the unstable boundary layer setting. Finally, we take the results of each approach and compare their surface flux variability: a baseline metric used in regional and global aerosol models.

Atmospheric particle abundance and sea salt aerosol observations in the springtime Arctic: a focus on blowing snow and leads

Abstract. Sea salt aerosols play an important role in the radiation budget and atmospheric composition over the Arctic, where the climate is rapidly changing. Previous observational studies have shown that Arctic sea ice leads are an important source of sea salt aerosols, and modeling efforts have also proposed blowing snow sublimation as a source. In this study, size-resolved atmospheric particle number concentrations and chemical composition were measured at the Arctic coastal tundra site of Utqiaġvik, Alaska, during spring (3 April–7 May 2016). Blowing snow conditions were observed during 25 % of the 5-week study period and were overpredicted by a commonly used blowing snow parameterization based solely on wind speed and temperature. Throughout the study, open leads were present locally. During periods when blowing snow was observed, significant increases in the number concentrations of 0.01–0.06 µm particles (factor of 6, on average) and 0.06–0.3 µm particles (67 %, on average) and a significant decrease (82 %, on average) in 1–4 µm particles were observed compared to low wind speed periods. These size distribution changes were likely caused by the generation of ultrafine particles from leads and/or blowing snow, with scavenging of supermicron particles by blowing snow. At elevated wind speeds, both submicron and supermicron sodium and chloride mass concentrations were enhanced, consistent with wind-dependent local sea salt aerosol production. At moderate wind speeds below the threshold for blowing snow as well as during observed blowing snow, individual sea spray aerosol particles were measured. These individual salt particles were enriched in calcium relative to sodium in seawater due to the binding of this divalent cation with organic matter in the sea surface microlayer and subsequent enrichment during seawater bubble bursting. The chemical composition of the surface snowpack also showed contributions from sea spray aerosol deposition. Overall, these results show the contribution of sea spray aerosol production from leads on both aerosols and the surface snowpack. Therefore, if blowing snow sublimation contributed to the observed sea salt aerosol, the snow being sublimated would have been impacted by sea spray aerosol deposition rather than upward brine migration through the snowpack. Sea spray aerosol production from leads is expected to increase, with thinning and fracturing of sea ice in the rapidly warming Arctic.

Ice-nucleating agents in sea spray aerosol identified and quantified with a holistic multimodal freezing model.

Sea spray aerosol (SSA) is a widely recognized important source of ice-nucleating particles (INPs) in the atmosphere. However, composition-specific identification, nucleation processes, and ice nucleation rates of SSA-INPs have not been well constrained. Microspectroscopic characterization of ambient and laboratory-generated SSA confirms that water-borne exudates from planktonic microorganisms composed of a mixture of proteinaceous and polysaccharidic compounds act as ice-nucleating agents (INAs). These data and data from previously published mesocosm and wave channel studies are subsequently used to further develop the stochastic freezing model (SFM) producing ice nucleation rate coefficients for SSA-INPs. The SFM simultaneously predicts immersion freezing and deposition and homogeneous ice nucleation by SSA particles under tropospheric conditions. Predicted INP concentrations agree with ambient and laboratory measurements. In addition, this holistic freezing model is independent of the source and exact composition of the SSA particles, making it well suited for implementation in cloud and climate models.

Probing Individual Particles Generated at the Freshwater-Seawater Interface through Combined Raman, Photothermal Infrared, and X-ray Spectroscopic Characterization.

Sea spray aerosol (SSA) is one of the largest global sources of atmospheric aerosol, but little is known about SSA generated in coastal regions with salinity gradients near estuaries and river outflows. SSA particles are chemically complex with substantial particle-to-particle variability due to changes in water temperature, salinity, and biological activity. In previous studies, the ability to resolve the aerosol composition to the level of individual particles has proven necessary for the accurate parameterization of the direct and indirect aerosol effects; therefore, measurements of individual SSA particles are needed for the characterization of this large source of atmospheric aerosol. An integrated analytical measurement approach is required to probe the chemical composition of individual SSA particles. By combining complementary vibrational microspectroscopic (Raman and optical photothermal infrared, O-PTIR) measurements with elemental information from computer-controlled scanning electron microscopy with energy-dispersive X-ray analysis (CCSEM-EDX), we gained unique insights into the individual particle chemical composition and morphology. Herein, we analyzed particles from four experiments on laboratory-based SSA production using coastal seawater collected in January 2018 from the Gulf of Maine. Individual salt particles were enriched in organics compared to that in natural seawater, both with and without added microalgal filtrate, with greater enrichment observed for smaller particle sizes, as evidenced by higher carbon/sodium ratios. Functional group analysis was carried out using the Raman and infrared spectra collected from individual SSA particles. Additionally, the Raman spectra were compared with a library of Raman spectra consisting of marine-derived organic compounds. Saccharides, followed by fatty acids, were the dominant components of the organic coatings surrounding the salt cores of these particles. This combined Raman, infrared, and X-ray spectroscopic approach will enable further understanding of the factors determining the individual particle composition, which is important for understanding the impacts of SSA produced within estuaries and river outflows, as well as areas of snow and ice melt.

Enrichment of short-chain organic acids transferred to submicron sea spray aerosols

Organic acids, considered to be a substantial component of the marine carbon cycle, can enter the atmosphere through sea spray aerosol (SSA) and further affect the climate. Despite their importance, the distribution and mixing state of organic acids in SSA over the marine boundary layer are poorly understood and therefore need more investigation. Here, we have used ion chromatography (IC) in anion mode to measure short-chain organic acids concentrations in SSA collected throughout a custom-made SSA simulation chamber. The enrichment behavior and morphology of monocarboxylic acids (MAs, C1–8) and dicarboxylic acids (DAs) in submicron SSA were studied in seawater. We found that with MAs addition, the number concentration and mass concentration of SSA particles decreased gradually for C5–8 MAs, whereas they weakly varied with DAs addition due to the fact that carboxyl groups at both ends of DAs increased the surface tension of seawater. Moreover, the target compounds in submicron SSA displayed a surface activity-dependent enrichment behavior, where seawater with stronger surface activity, such as that containing MAs with >5 carbons, was more enriched in SSA in comparison to seawater with weaker surface activity. MAs with chain length <5 carbons were slightly enriched in SSA, whereas the enrichment factor (EF) of C5–8 MAs further increased with increasing chain length. These findings are of utmost importance in further understanding and quantifying the contribution of organic matter to SSA, which is crucial for assessing the atmosphere feedback of the marine carbon cycle. Main finding of the workSurface tension of seawater is the key factor affecting the enrichment of short-chain organic acids in SSA.

Factors controlling the transfer of biogenic organic species from seawater to sea spray aerosol

Ocean waves transfer sea spray aerosol (SSA) to the atmosphere, and these SSA particles can be enriched in organic matter relative to salts compared to seawater ratios. A fundamental understanding of the factors controlling the transfer of biogenic organic matter from the ocean to the atmosphere remains elusive. Field studies that focus on understanding the connection between organic species in seawater and SSA are complicated by the numerous processes and sources affecting the composition of aerosols in the marine environment. Here, an isolated ocean–atmosphere system enables direct measurements of the sea–air transfer of different classes of biogenic organic matter over the course of two phytoplankton blooms. By measuring excitation–emission matrices of bulk seawater, the sea surface microlayer, and SSA, we investigate time series of the transfer of fluorescent species including chlorophyll-a, protein-like substances, and humic-like substances. Herein, we show the emergence of different molecular classes in SSA at specific times over the course of a phytoplankton bloom, suggesting that SSA chemical composition changes over time in response to changing ocean biological conditions. We compare the temporal behaviors for the transfer of each component, and discuss the factors contributing to differences in transfer between phases.

Heterogeneous ice nucleation ability of aerosol particles generated from Arctic sea surface microlayer and surface seawater samples at cirrus temperatures

Abstract. Sea spray aerosol particles are a recognised type of ice-nucleating particles under mixed-phase cloud conditions. Entities that are responsible for the heterogeneous ice nucleation ability include intact or fragmented cells of marine microorganisms as well as organic matter released by cell exudation. Only a small fraction of sea spray aerosol is transported to the upper troposphere, but there are indications from mass-spectrometric analyses of the residuals of sublimated cirrus particles that sea salt could also contribute to heterogeneous ice nucleation under cirrus conditions. Experimental studies on the heterogeneous ice nucleation ability of sea spray aerosol particles and their proxies at temperatures below 235 K are still scarce. In our article, we summarise previous measurements and present a new set of ice nucleation experiments at cirrus temperatures with particles generated from sea surface microlayer and surface seawater samples collected in three different regions of the Arctic and from a laboratory-grown diatom culture (Skeletonema marinoi). The particles were suspended in the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) cloud chamber and ice formation was induced by expansion cooling. We confirmed that under cirrus conditions, apart from the ice-nucleating entities mentioned above, also crystalline inorganic salt constituents can contribute to heterogeneous ice formation. This takes place at temperatures below 220 K, where we observed in all experiments a strong immersion freezing mode due to the only partially deliquesced inorganic salts. The inferred ice nucleation active surface site densities for this nucleation mode reached a maximum of about 5×1010 m−2 at an ice saturation ratio of 1.3. Much smaller densities in the range of 108–109 m−2 were observed at temperatures between 220 and 235 K, where the inorganic salts fully deliquesced and only the organic matter and/or algal cells and cell debris could contribute to heterogeneous ice formation. These values are 2 orders of magnitude smaller than those previously reported for particles generated from microlayer suspensions collected in temperate and subtropical zones. While this difference might simply underline the strong variability of the number of ice-nucleating entities in the sea surface microlayer across different geographical regions, we also discuss how instrumental parameters like the aerosolisation method and the ice nucleation measurement technique might affect the comparability of the results amongst different studies.

Sources, Occurrence and Characteristics of Fluorescent Biological Aerosol Particles Measured Over the Pristine Southern Ocean.

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.

Cation-Driven Lipopolysaccharide Morphological Changes Impact Heterogeneous Reactions of Nitric Acid with Sea Spray Aerosol Particles.

Lipopolysaccharides (LPS) in sea spray aerosol (SSA) particles have recently been shown to undergo heterogeneous reactions with HNO3 in the atmosphere. Here, we integrate theory and experiment to further investigate how the most abundant sea salt cations, Na+, Mg2+, and Ca2+, impact HNO3 reactions with LPS-containing SSA particles. Aerosol reaction flow tube studies show that heterogeneous reactions of SSA particles with divalent cation (Mg2+ and Ca2+) and LPS signatures were less reactive with HNO3 than those dominated by monovalent cations (Na+). All-atom molecular dynamics simulations of model LPS aggregates suggest that divalent cations cross-link the oligosaccharide chains to increase molecular aggregation and rigidity, which changes the particle phase and morphology, decreases water diffusion, and consequently decreases the reactive uptake of HNO3. This study provides new insight into how complex chemical interactions between ocean-derived salts and biogenic organic species can impact the heterogeneous reactivity of SSA particles.

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

Free (FAAs) and combined amino acids (CAAs) were investigated on size-resolved samples of nascent sea spray aerosol (SSA) particles generated during controlled laboratory experiments. Compared to seawater, the amino acids were strongly enriched on the SSA particles. The enrichment factors (EFaer) on submicron SSA particles (EFaer∑FAA: 2.5 × 106 and EFaer∑CAA: 7.9 × 105) were 1–2 orders of magnitude higher than on supermicron ones (EFaer∑FAA: 1.0 × 105 and EFaer∑CAA: 7.3 × 104) and continuously increased toward smaller SSA particles. Molecular-level analysis showed that the more polar the FAAs, the more they are enriched on the SSA particles (especially FAAs with polar acid side chains, e.g., aspartic acid: EFaer of 5.8 × 106). Comparison of the amino acids present on nascent SSA with those present on ambient marine aerosol particles revealed a higher complexity of the amino acids of the nascent SSA, suggesting that atmospheric processes likely reduce the amino acid diversity. In addition, our results highlight that although almost all the amino acids studied are transferred to the atmosphere via bubble bursting under controlled conditions, two amino acids, γ-aminobutyric acid (GABA) and glycine likely have additional sources to the atmosphere. GABA is likely formed on ambient marine submicron aerosol particles to a large extent (35–47% of ∑FAA). Glycine likely originates from long-range transport processes or photochemical reactions, as discussed in the literature; however, our results highlight the potential for a direct oceanic source via bubble bursting (∼20% of ∑FAA). Overall, bubble-bursting-derived total amino acids made up 11–18% of the mass of dissolved organic carbon on the submicron SSA particles.

Measurement report: Ice nucleating abilities of biomass burning, African dust, and sea spray aerosol particles over the Yucatán Peninsula

Abstract. Most precipitation from deep clouds over the continents and in the intertropical convergence zone is strongly influenced by the presence of ice crystals whose formation requires the presence of ice nucleating particles (INPs). Although there are a large number of INP sources, the ice nucleating abilities of aerosol particles originating from oceans, deserts, and wildfires are poorly described at tropical latitudes. To fill this gap in knowledge, the National Autonomous University of Mexico micro-orifice uniform deposit impactor droplet freezing technique (UNAM-MOUDI-DFT) was constructed to measure the ice nucleating activity of aerosol samples that were collected in Sisal and Mérida, Yucatán (Mexico) under the influence of cold fronts, biomass burning (BB), and African dust (AD) intrusions during five short-term field campaigns between January 2017 and July 2018. The three different aerosol types were distinguished by their physicochemical properties. Marine aerosol (MA), BB, and AD air masses were found to contain INPs; the highest concentrations were in AD (from 0.071 to 36.07 L−1 at temperatures between −18 and −27 ∘C), followed by MA (from 0.068 to 18.90 L−1 at temperatures between −15 and −28 ∘C) and BB (from 0.063 to 10.21 L−1 at temperatures between −20 and −27 ∘C). However, MA had the highest surface active site densities (ns) between −15 and −30 ∘C. Additionally, supermicron particles contributed more than 72 % of the total INP concentration independent of aerosol type.

Tandem Fluorescence Measurements of Organic Matter and Bacteria Released in Sea Spray Aerosols

Biological aerosols, typically identified through their fluorescence properties, strongly influence clouds and climate. Sea spray aerosol (SSA) particles are a major source of biological aerosols, but detection in the atmosphere is challenging due to potential interference from other sources. Here, the fluorescence signature of isolated SSA, produced using laboratory-based aerosol generation methods, was analyzed and compared with two commonly used fluorescence techniques: excitation-emission matrix spectroscopy (EEMS) and the wideband integrated bioaerosol sensor (WIBS). A range of dynamic biological ocean scenarios were tested to compare EEMS and WIBS analyses of SSA. Both techniques revealed similar trends in SSA fluorescence intensity in response to changes in ocean microbiology, demonstrating the potential to use the WIBS to measure fluorescent aerosols alongside EEMS bulk solution measurements. Together, these instruments revealed a unique fluorescence signature of isolated, nascent SSA and, for the first time, a size-segregated emission of fluorescent species in SSA. Additionally, the fluorescence signature of aerosolized marine bacterial isolates was characterized and showed similar fluorescence peaks to those of SSA, suggesting that bacteria are a contributor to SSA fluorescence. Through investigation of isolated SSA, this study provides a reference for future identification of marine biological aerosols in a complex atmosphere.

Wind, waves, and surface currents in the Southern Ocean: observations from the Antarctic Circumnavigation Expedition

Abstract. The Southern Ocean has a profound impact on the Earth's climate system. Its strong winds, intense currents, and fierce waves are critical components of the air–sea interface and contribute to absorbing, storing, and releasing heat, moisture, gases, and momentum. Owing to its remoteness and harsh environment, this region is significantly undersampled, hampering the validation of prediction models and large-scale observations from satellite sensors. Here, an unprecedented data set of simultaneous observations of winds, surface currents, and ocean waves is presented, to address the scarcity of in situ observations in the region – https://doi.org/10.26179/5ed0a30aaf764 (Alberello et al., 2020c) and https://doi.org/10.26179/5e9d038c396f2 (Derkani et al., 2020). Records were acquired underway during the Antarctic Circumnavigation Expedition (ACE), which went around the Southern Ocean from December 2016 to March 2017 (Austral summer). Observations were obtained with the wave and surface current monitoring system WaMoS-II, which scanned the ocean surface around the vessel using marine radars. Measurements were assessed for quality control and compared against available satellite observations. The data set is the most extensive and comprehensive collection of observations of surface processes for the Southern Ocean and is intended to underpin improvements of wave prediction models around Antarctica and research of air–sea interaction processes, including gas exchange and dynamics of sea spray aerosol particles. The data set has further potentials to support theoretical and numerical research on lower atmosphere, air–sea interface, and upper-ocean processes.