Gas exchange reduction (GER) at the air-sea interface is positively related to the concentration of organic matter (OM) in the top centimetre of the ocean, as well as to phytoplankton abundance and primary production. The mechanisms relating OM to GER remain unclear, but may involve mechanical (rheological) damping of turbulence in the water immediately below the surface microlayer, damping of ripples and blocking of molecular diffusion by layers of OM, as well as electrical effects. To help guide future research in GER, particularly of CO 2 , we review published rheological properties of ocean water and cultures of phytoplankton and bacteria in both 3D and 2D deformation geometries, in water from both the surface layer and underlying water. Production of foam modulates air-sea exchange of many properties and substances, perhaps including climate-changing gases such as CO 2 . We thus also review biological modulation of production and decay of whitecaps and other sea foam. In the ocean literature on biological production of OM, particularly that which associates with the sea surface, the terms “surfactant” and “surface-active” have been given a variety of meanings that are sometimes vague, and may confuse. We therefore propose a more restricted definition of these terms in line with usage in surface science and organic chemistry. Finally, possible changes in OM-modulated GER are presented in relation to predicted global environmental changes.

We investigated the influence of solar radiation on biogeochemical parameters of the sea surface microlayer (SML), including the spectroscopic composition of FDOM, and biotic and abiotic parameters. We calculated the humification index, biological index, and recently produced material index from the ultraviolet spectra to characterize the dynamic environment of the SML. The humification index ranged from 4 to 14 in the SML and 14 to 22 in underlying water (ULW). An inverse relation for this index as a function of solar radiation was observed, indicating photochemical decomposition of complex molecules present in fluorescent dissolved organic matter (FDOM). The biological index (along Leg 2) ranged from 1.0 to 2.0 for the SML and 1.0 to 1.5 for ULW. The index for recently produced material ranged from 0.25 to 0.8 for the SML and 0.5 to 1.0 for ULW. The FDOM enrichment process of the SML was influenced by the photochemical decomposition of highly aromatic-like fluorophores, as indicated by the calculated indices. Fluorescence intensity increased for humic C peaks (>0.5 Raman units) in the North Sea samples and for humic M peaks (>1.0 Raman units) for Jade Bay. Spearman analysis for FDOM enrichment in the SML as a function of PAR (for Leg 2) showed a weak positive correlation (Rho = 0.676, n = 11, p = 0.022). Abundance of small photoautotrophic cells (Rho = 0.782, n = 11, p = 0.045) and of bacteria (Rho = 0.746, n = 11, p = 0.0082) also showed a positive correlation as a function of PAR. Overall, we found positive trends between the intensity of available light and the response of the constituents within the SML, highlighting the role of the surface microlayer as a distinctive habitat characterized by unique photochemical processes.

Understanding how the ocean absorbs anthropogenic CO 2 is critical for predicting climate change. We designed Sniffle , a new autonomous drifting buoy with a floating chamber, to measure gas transfer velocities and air–sea CO 2 fluxes with high spatiotemporal resolution. Currently, insufficient in situ data exist to verify gas transfer parameterizations at low wind speeds (<4 m s –1 ), which leads to underestimation of gas transfer velocities and, therefore, of air–sea CO 2 fluxes. The Sniffle is equipped with a sensor to consecutively measure aqueous and atmospheric p CO 2 and to monitor increases or decreases of CO 2 inside the chamber. During autonomous operation, a complete cycle lasts 40 minutes, with a new cycle initiated after flushing the chamber. The Sniffle can be deployed for up to 15 hours at wind speeds up to 10 m s –1 . Floating chambers often overestimate fluxes because they create additional turbulence at the water surface. We correct fluxes by measuring turbulence with two acoustic Doppler velocimeters, one positioned directly under the floating chamber and the other positioned sideways, to compare artificial disturbance caused by the chamber and natural turbulence. The first results of deployment in the North Sea during the summer of 2016 demonstrate that the new drifting buoy is a useful tool that can improve our understanding of gas transfer velocity with in situ measurements. At low and moderate wind speeds and different conditions, the results obtained indicate that the observed tidal basin was acting as a source of atmospheric CO 2 . Wind speed and turbulence alone could not fully explain the variance in gas transfer velocity. We suggest that other factors like surfactants, rain or tidal current will have an impact on gas transfer parameterizations.

Increasing human activity has raised concerns about the impact of deposition of anthropogenic combustion aerosols (i.e., black carbon; BC) on marine processes. The sea surface microlayer (SML) is a key gate for the introduction of atmospheric BC into the ocean; however, relatively little is known of the effects of BC on bacteria-virus interactions, which can strongly influence microbially mediated processes. To study the impact of BC on bacteria-virus interactions, field investigations involving collection from the SML and underlying water were carried out in Halong Bay (Vietnam). Most inorganic nutrient concentrations, as well as dissolved organic carbon, were modestly but significantly higher ( p = 0.02–0.05) in the SML than in underlying water. The concentrations of particulate organic carbon (though not chlorophyll a ) and of total particulate carbon, which was composed largely of particulate BC (mean = 1.7 ± 6.4 mmol L –1 ), were highly enriched in the SML, and showed high variability among stations. On average, microbial abundances (both bacteria and viruses) and bacterial production were 2- and 5fold higher, respectively, in the SML than in underlying water. Significantly lower bacterial production ( p < 0.01) was observed in the particulate fraction (>3 µm) compared to the bulk sample, but our data overall suggest that bacterial production in the SML was stimulated by particulate BC. Higher bacterial production in the SML than in underlying water supported high viral lytic infection rates (from 5.3 to 30.1%) which predominated over percent lysogeny (from undetected to 1.4%). The sorption of dissolved organic carbon by black carbon, accompanied by the high lytic infection rate in the black carbon-enriched SML, may modify microbially mediated processes and shift the net ecosystem metabolism (ratio of production and respiration) to net heterotrophy and CO 2 production in this critical layer between ocean and atmosphere.

The damping of short gravity-capillary waves (Bragg waves) due to surfactant accumulation under low wind speed conditions results in the formation of natural sea slicks. These slicks are detectable visually and in synthetic aperture radar satellite imagery. Surfactants are produced by natural life processes of many marine organisms, including bacteria, phytoplankton, seaweed, and zooplankton. In this work, samples were collected in the Gulf of Mexico during a research cruise on the R/V F.G. Walton Smith to evaluate the relative abundance of Bacillus spp., surfactant-associated bacteria, in the sea surface microlayer compared to the subsurface water at 0.2 m depth. A method to reduce potential contamination of microlayer samples during their collection on polycarbonate filters was implemented and advanced, including increasing the number of successive samples per location and changing sample storage procedures. By using DNA analysis (real-time polymerase chain reaction) to target Bacillus spp., we found that in the slick areas, these surfactant-associated bacteria tended to reside mostly in subsurface waters, lending support to the concept that the surfactants they may produce move to the surface where they accumulate under calm conditions and enrich the sea surface microlayer.

Emissions of black carbon (BC), a product of incomplete combustion of fossil fuels, biofuels and biomass, are high in the Asia-Pacific region, yet input pathways and rates to the ocean are not well constrained. Atmospheric and riverine inputs of BC in Halong Bay (Vietnam), a hotspot of atmospheric BC, were studied at monthly intervals during one year. Climate in Halong Bay is governed by the monsoon regime, characterized by a northeast winter monsoon (dry season) and southeast summer monsoon (wet season). During the dry season, atmospheric BC concentrations averaged twice those observed during the wet season. In the sea surface microlayer (SML) and underlying water (ULW), concentrations of particulate BC (PBC) averaged 539 and 11 µmol C L –1 , respectively. Dissolved BC (DBC) concentrations averaged 2.6 µmol C L –1 in both the SML and ULW. Seasonal variations indicated that PBC concentration in the SML was controlled by atmospheric deposition during the dry season, while riverine inputs controlled both PBC and DBC concentrations in ULW during the wet season. Spatiotemporal variations of PBC and DBC during the wet season suggest that river runoff was efficient in transporting PBC that had accumulated on land during the dry season, and in mobilizing and transporting DBC to the ocean. The annual river flux of PBC was about 3.8 times higher than that of DBC. The monsoon regime controls BC input to Halong Bay by favoring dry deposition of BC originating from the north during the dry season, and wet deposition and river runoff during the wet season. High PBC concentrations seem to enhance the transfer of organic carbon from dissolved to particulate phase by adsorbing dissolved organic carbon and stimulating aggregation. Such processes may impact the availability and biogeochemical cycling of other dissolved substances, including nutrients, for the coastal marine ecosystem.

Enrichment of fluorescence dissolved organic matter (FDOM) in the sea surface microlayer (SML) provides insights into biogeochemical processes occurring at the sea surface, including cycling of organic matter, photochemistry, and air-sea gas exchange. We present data concerning the variability of FDOM enrichment in the SML during upwelling events in the Baltic Sea (Cruise M117). Our results show that FDOM is frequently enriched (75% of all samples) and that enrichment factors are significantly higher in SMLs located in regions with upwelling (pooled median = 1.4) compared to a non-upwelling region (median = 1.1). The enrichment factor of FDOM showed short time-scale variability, changing by 6% within ten-minute intervals. Larger variabilities (standard deviation up to ±0.14 µg L –1 compared to background of ±0.01 µg L –1 ) occurred when fronts were present and when the SML was mixed with underlying bulk water. Small-scale patchiness, indicated by changes in the variability of FDOM enrichment in SML, was a common feature of the sea surface. Wind speed played a potential role in controlling the enrichment of FDOM in the SML, but the effects of solar radiation on photochemical processes, mixing and upwelling of water masses, and biological processes as a source of FDOM also influence enrichment at this critical interface between ocean and atmosphere.

Natural and anthropogenic aerosols are a significant source of trace elements to oligotrophic ocean surface waters, where they provide episodic pulses of limiting micronutrients for the microbial community. However, little is known about the fate of trace elements at the air-sea interface, i.e. the sea surface microlayer. In this study, samples of aerosols, sea surface microlayer, and underlying water column were collected in the Florida Keys during a dusty season (July 2014) and non-dusty season (May 2015) and analyzed for the dissolved and particulate elements Al, Fe, Ni, Cu, Zn, and Pb. Microlayer samples were collected using a cylinder of ultra-pure SiO 2 (quartz glass), a novel adaptation of the glass plate technique. A significant dust deposition event occurred during the 2014 sampling period which resulted in elevated concentrations of trace elements in the microlayer. Residence times in the microlayer from this event ranged from 12 to 94 minutes for dissolved trace elements and from 1.3 to 3.4 minutes for particulate trace elements. These residence times are potentially long enough for the atmospherically derived trace elements to undergo chemical and biological alterations within the microlayer. Characterizing the trace element distributions within the three regimes is an important step towards our overall goals of understanding the rates and mechanisms of the solubilization of trace elements following aeolian dust deposition and how this might affect microorganisms in surface waters.

The export of organic matter from ocean to atmosphere represents a substantial carbon flux in the Earth system, yet the impact of environmental drivers on this transfer is not fully understood. This work presents dissolved and particulate organic carbon (DOC, POC) concentrations, their enrichment factors in the sea surface microlayer (SML), and equivalent measurements in marine aerosol particles across the Atlantic Ocean. DOC concentrations averaged 161 ± 139 µmol L –1 (n = 78) in bulk seawater and 225 ± 175 µmol L –1 (n = 79) in the SML; POC concentrations averaged 13 ± 11 µmol L –1 (n = 80) and 17 ± 10 µmol L –1 (n = 80), respectively. High DOC and POC enrichment factors were observed when samples had low concentrations, and lower enrichments when concentrations were high. The impacts of wind speed and chlorophyll-a levels on concentrations and enrichment of DOC and POC in seawater were insignificant. In ambient submicron marine aerosol particles the concentration of water-soluble organic carbon was approximately 0.2 µg m –3 . Water-insoluble organic carbon concentrations varied between 0.01 and 0.9 µg m –3 , with highest concentrations observed when chlorophyll-a concentrations were high. Concerted measurements of bulk seawater, the SML and aerosol particles enabled calculation of enrichment factors of organic carbon in submicron marine ambient aerosols, which ranged from 10 3 to 10 4 during periods of low chlorophyll-a concentrations and up to 10 5 when chlorophyll-a levels were high. The results suggest that elevated local biological activity enhances the enrichment of marine-sourced organic carbon on aerosol particles. However, implementation of the results in source functions based on wind speed and chlorophyll-a concentrations underestimated the organic fraction at low biological activity by about 30%. There may be additional atmospheric and oceanic parameters to consider for accurately predicting organic fractions on aerosol particles.

The concentration of microbes and other particulates is frequently enriched in the droplets produced by bursting bubbles. As a bubble rises to the ocean surface, particulates in the bulk liquid can be transported to the sea surface microlayer by attaching to the bubble’s interface. When the bubble eventually ruptures, a fraction of these particulates is often ejected into the surroundings in film droplets with a particulate concentration that is higher than in the liquid from which they formed. The precise mechanisms responsible for this enrichment are unclear, yet such enrichment at the ocean surface influences important exchange processes with the atmosphere. Here we provide evidence that drainage, coupled with scavenging, is responsible for the enrichment. By simultaneously recording the drainage and rupture effects with high-speed and standard photography, we directly measured the particulate concentrations in the thin film of a bubble cap at the moment before it ruptures. We observed that the enrichment factor strongly depends on the film thickness at rupture, and developed a physical model, based on scavenging and drainage, that is consistent with our observations. We have also demonstrated that this model is quantitatively consistent with prior observations of film drop enrichment, indicating its potential for a broader range of applications in the study of the sea surface microlayer and related phenomena.

The sea surface microlayer (SML) is the boundary interface between the atmosphere and ocean, covering about 70% of the Earth’s surface. With an operationally defined thickness between 1 and 1000 µm, the SML has physicochemical and biological properties that are measurably distinct from underlying waters. Recent studies now indicate that the SML covers the ocean to a significant extent, and evidence shows that it is an aggregate-enriched biofilm environment with distinct microbial communities. Because of its unique position at the air-sea interface, the SML is central to a range of global biogeochemical and climate-related processes. The redeveloped SML paradigm pushes the SML into a new and wider context that is relevant to many ocean and climate sciences.