Effects of Natural and Artificial Surfactants on Diffusive Boundary Dynamics and Oxygen Exchanges across the Air–Water Interface

Comparing measurements of the natural sea surface microlayer (SML) and artificial surface films made of Triton-X-100 and oleyl alcohol can provide a fundamental understanding of diffusive gas fluxes across the air–water boundary layers less than 1 mm thick. We investigated the impacts of artificial films on the concentration gradients and diffusion of oxygen (O2) across the SML, the thickness of the diffusive boundary layer (DBL), and the surface tension levels of natural seawater and deionized water. Natural and artificial films led to approximately 78 and 81% reductions in O2 concentration across the surfaces of natural seawater and deionized water, respectively. The thicknesses of the DBL were 500 and 350 µm when natural SML was added on filtered and unfiltered natural seawater, respectively, although the DBL on filtered seawater was unstable, as indicated by decreasing thickness over time. Triton-X-100 and oleyl alcohol at a concentration of 2000 µg L−1 in deionized water persistently increased the DBL thickness values by 30 and 26% over a period of 120 min. At the same concentration, Triton-X-100 and oleyl alcohol decreased the surface tension of deionized water from ~72 mN m−1 to 48 and 38 mN m−1, respectively; 47% recovery was recorded after 30 min with Triton-X-100, although low surface tension persisted for 120 min with oleyl alcohol. The critical micelle concentration values of Triton-X-100 ranged between 400 and 459 µg L−1. We, therefore, suggest that Triton-X-100 resembles natural SML because the reduction and partial recovery of the surface tension of deionized water with the surfactant resembles the behavior observed for natural slicks. Temperature and salinity were observed to linearly decrease the surface tension levels of natural seawater, artificial seawater, and deionized water. Although several factors leading to O2 production and consumption in situ are excluded, experiments carried out under laboratory-controlled conditions are useful for visualizing fine-scale processes of O2 transfer from water bodies through the surface microlayer.

Occurrence and Distribution of Polycyclic Aromatic Hydrocarbons in the Marine Surface Microlayer of an Industrialized Coastal Area in the Eastern Mediterranean

Concentrations of dissolved and particulate polycyclic aromatic hydrocarbons (PAHs) were determined seasonally in sea surface microlayer (SML) and sub-surface water (SSW) within the Saronicos Gulf, Greece, close to a highly industrialized coastal zone. For the 16 US EPA priority PAHs, the sum of dissolved PAHs (∑dPAHs) concentrations ranged from 40.4 to 237 ng L−1 in SML, 22.8–180 ng L−1 in SSW0.2, whereas the corresponding concentrations in suspended particulate matter (∑pPAHs) were 30.8 to 177 ng L−1 and 36.8–171 ng L−1, respectively. The enrichment factor (EF) for dissolved ∑dPAHs varied from 0.9 to 2.1 with a mean value of 1.5 (n = 10) being statistically significantly greater than unity, whereas for particulate ∑pPAHs, no enrichment of the SML was reported. Enrichment factors of 5–6 ring PAHs were higher near the industrial zone. The possible sources, fate, and toxicity of PAHs are also discussed.

Compound jetting from bubble bursting at an air-oil-water interface

Bursting of bubbles at a liquid surface is ubiquitous in a wide range of physical, biological, and geological phenomena, as a key source of aerosol droplets for mass transport across the interface. However, how a structurally complex interface, widely present in nature, mediates the bursting process remains largely unknown. Here, we document the bubble-bursting jet dynamics at an oil-covered aqueous surface, which typifies the sea surface microlayer as well as an oil spill on the ocean. The jet tip radius and velocity are altered with even a thin oil layer, and oily aerosol droplets are produced. We provide evidence that the coupling of oil spreading and cavity collapse dynamics results in a multi-phase jet and the follow-up droplet size change. The oil spreading influences the effective viscous damping, and scaling laws are proposed to quantify the jetting dynamics. Our study not only advances the fundamental understanding of bubble bursting dynamics, but also may shed light on the airborne transmission of organic matters in nature related to aerosol production.

Variability of the Sea Surface Microlayer Across a Filament’s Edge and Potential Influences on Gas Exchange

Major uncertainties in air-sea gas flux parameterizations may arise from a yet unpredictable sea surface microlayer (SML). Its influence on gas exchange is twofold as organic matter, in particular surfactants, on one side and organisms enriched in the SML on the other can alter air-sea gas fluxes. However, spatial heterogeneity of the SML and its potential consequences for gas exchange are not well understood. This study examines the SML’s surfactant pool and the dynamics of microbial enrichment across the sharp hydrological front of a newly upwelled filament off Mauritania. The front was marked by a distinct decrease in temperature and salinity compared to the stratified water column outside the filament. Distinct chemical and microbial SML properties were observed and associated with the filament. Overall, organic matter in the SML was significantly higher concentrated inside the filament and in equivalence to the underlying water. Degradation indices derived from total amino acids (TAA) composition indicated production of fresh organic matter inside and increased degradation outside the filament. Moreover, a shift in the microbial community was observed, for instance Synechococcus spp. prevailed outside the filament. Autotrophic and heterotrophic microorganisms preferably colonized the SML outside the filament. Organic matter enrichment in the SML depended largely on the chemical nature of biomolecules. Total organic carbon (TOC), total nitrogen and total combined carbohydrates were only slightly enriched while glucose, TAA and surfactants were considerably enriched in the SML. Surfactant concentration was positively correlated to TAA, in particular to arginine and glutamic acid, indicating that fresh organic matter components enhanced surface activity. Further, TOC and surfactant concentration correlated significantly (r2 = 0.47, p-value < 0.001). The lower limit of this linear correlation hits approximately the lowest TOC concentration expected within the global surface ocean. This suggests that surfactants are primarily derived from autochthonous production and most refractory components are excluded. Using a previously established relationship between surfactants and CO2 gas exchange (Pereira et al., 2018), we estimated that surfactants suppressed gas exchange by 12% inside the filament. This could be of relevance for freshly upwelled filaments, which are often supersaturated in greenhouse gases.

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

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.

Terrestrial or marine – indications towards the origin of ice-nucleating particles during melt season in the European Arctic up to 83.7° N

Ice-nucleating particles (INPs) initiate the primary ice formation in clouds at temperatures above ca. −38 ∘C and have an impact on precipitation formation, cloud optical properties, and cloud persistence. Despite their roles in both weather and climate, INPs are not well characterized, especially in remote regions such as the Arctic. We present results from a ship-based campaign to the European Arctic during May to July 2017. We deployed a filter sampler and a continuous-flow diffusion chamber for offline and online INP analyses, respectively. We also investigated the ice nucleation properties of samples from different environmental compartments, i.e., the sea surface microlayer (SML), the bulk seawater (BSW), and fog water. Concentrations of INPs (NINP) in the air vary between 2 to 3 orders of magnitudes at any particular temperature and are, except for the temperatures above −10 ∘C and below −32 ∘C, lower than in midlatitudes. In these temperature ranges, INP concentrations are the same or even higher than in the midlatitudes. By heating of the filter samples to 95 ∘C for 1 h, we found a significant reduction in ice nucleation activity, i.e., indications that the INPs active at warmer temperatures are biogenic. At colder temperatures the INP population was likely dominated by mineral dust. The SML was found to be enriched in INPs compared to the BSW in almost all samples. The enrichment factor (EF) varied mostly between 1 and 10, but EFs as high as 94.97 were also observed. Filtration of the seawater samples with 0.2 µm syringe filters led to a significant reduction in ice activity, indicating the INPs are larger and/or are associated with particles larger than 0.2 µm. A closure study showed that aerosolization of SML and/or seawater alone cannot explain the observed airborne NINP unless significant enrichment of INP by a factor of 105 takes place during the transfer from the ocean surface to the atmosphere. In the fog water samples with −3.47 ∘C, we observed the highest freezing onset of any sample. A closure study connecting NINP in fog water and the ambient NINP derived from the filter samples shows good agreement of the concentrations in both compartments, which indicates that INPs in the air are likely all activated into fog droplets during fog events. In a case study, we considered a situation during which the ship was located in the marginal sea ice zone and NINP levels in air and the SML were highest in the temperature range above −10 ∘C. Chlorophyll a measurements by satellite remote sensing point towards the waters in the investigated region being biologically active. Similar slopes in the temperature spectra suggested a connection between the INP populations in the SML and the air. Air mass history had no influence on the observed airborne INP population. Therefore, we conclude that during the case study collected airborne INPs originated from a local biogenic probably marine source.