Size-Dependent Nascent Sea Spray Aerosol Bounce Fractions and Estimated Viscosity: The Role of Divalent Cation Enrichment, Surface Tension, and the Kelvin Effect.

Viscosity, or the "thickness," of aerosols plays a key role in atmospheric processes like ice formation, water absorption, and heterogeneous kinetics. However, the viscosity of sea spray aerosols (SSA) has not been widely studied. This research explored the relationship between particle size and viscosity of authentic SSA particles through particle bounce, atomic force microscopy analysis, and predictive viscosity modeling from molecular composition. The study found that 40 nm SSA particles had estimated viscosities around 104 Pa·s and bounce fractions three times higher than 100 and 200 nm particles with less than 102 Pa·s at a relative humidity (RH) of 60%. Additional studies revealed the Kelvin effect and particle density, influenced by particle size, have a greater impact on size-dependent bounce fractions than changes in RH across impactor stages. While changes in the level of surfactants can impact particle bounce, the increased viscosity in smaller SSA is attributed to the formation of gel-like phase states caused by cation-organic cross-links between divalent calcium ions and organic anions enriched in the smaller particles. This work shows the smallest gel-like SSA particles observed in the field are highly viscous, which has implications for cloud formation, secondary aerosol growth, and pollutant transport in coastal environments.

Effects of Wind Speed on Size-Dependent Morphology and Composition of Sea Spray Aerosols.

Variable wind speeds over the ocean can have a significant impact on the formation mechanism and physical-chemical properties of sea spray aerosols (SSA), which in turn influence their climate-relevant impacts. Herein, for the first time, we investigate the effects of wind speed on size-dependent morphology and composition of individual nascent SSA generated from wind-wave interactions of natural seawater within a wind-wave channel as a function of size and their particle-to-particle variability. Filter-based thermal optical analysis, atomic force microscopy (AFM), AFM infrared spectroscopy (AFM-IR), and scanning electron microscopy (SEM) were employed in this regard. This study focuses on SSA with sizes within 0.04-1.8 µm generated at two wind speeds: 10 m/s, representing a wind lull scenario over the ocean, and 19 m/s, indicative of the wind speeds encountered in stormy conditions. Filter-based measurements revealed a reduction of the organic mass fraction as the wind speed increases. AFM imaging at 20% relative humidity of individual SSA identified six main morphologies: prism-like, rounded, core-shell, rod, rod inclusion core-shell, and aggregates. At 10 m/s, most SSA were rounded, while at 19 m/s, core-shells became predominant. Based on AFM-IR, rounded SSA at both wind speeds had similar composition, mainly composed of aliphatic and oxygenated species, whereas the shells of core-shells displayed more oxygenated organics at 19 m/s and more aliphatic organics at 10 m/s. Collectively, our observations can be attributed to the disruption of the sea surface microlayer film structure at higher wind speeds. The findings reveal a significant impact of wind speed on morphology and composition of SSA, which should be accounted for accurate assessment of their climate effects.

A deep learning method for reflective boundary estimation.

Environment estimation is a challenging task in reverberant settings such as the underwater and indoor acoustic domains. The locations of reflective boundaries, for example, can be estimated using acoustic echoes and leveraged for subsequent, more accurate localization and mapping. Current boundary estimation methods are constrained to high signal-to-noise ratios or are customized to specific environments. Existing methods also often require a correct assignment of echoes to boundaries, which is difficult if spurious echoes are detected. To evade these limitations, a convolutional neural network (NN) method is developed for robust two-dimensional boundary estimation, given known emitter and receiver locations. A Hough transform-inspired algorithm is leveraged to transform echo times of arrival into images, which are amenable to multi-resolution regression by NNs. The same architecture is trained on transform images of different resolutions to obtain diverse NNs, deployed sequentially for increasingly refined boundary estimation. A correct echo labeling solution is not required, and the method is robust to reverberation. The proposed method is tested in simulation and for real data from a water tank, where it outperforms state-of-the-art alternatives. These results are encouraging for the future development of data-driven three-dimensional environment estimation with high practical value in underwater acoustic detection and tracking.

Depth-dependence of the underwater noise emission from melting glacier ice.

Submarine-melting of ice at the glacier-ocean interface accounts for a large portion of the ice-loss at tidewater glaciers and produces sound via bubble-release. The sound production is dominant in the sub-surface region near the glacier-ocean interface. This depth-dependence of the sound is studied by melting ice blocks in a glacial bay at various depths up to 20 m and recording their acoustics over a large frequency range. The acoustic energy decreases with depth in line with expectations from the physics of the phenomenon and is fit to an exponentially decaying curve. The estimated variation will be useful for interpreting the sound in marine-terminating glaciers bays in terms of the submarine-melting activity.

An architecture for passive joint localization and structure learning in reverberant environments.

Passive localization and tracking of a mobile emitter, and joint learning of its reverberant three-dimensional (3D) acoustic environment, where critical structural features are unknown, is a key open problem. Unaccounted-for occluders are potentially present, so that the emitter can lose line-of-sight to the receivers, and can only be observed through its reflected raypaths. The locations of reflective boundaries must therefore be jointly estimated with the emitter's position. A multistage global optimization and tracking architecture is developed to solve this problem with a relatively unconstrained model. Each stage of this architecture establishes domain knowledge such as synchronization and initial environment estimation, which are inputs for the following stages of more refined algorithms. This approach is generalizable to different physical scales and modalities and improves on methods that do not exploit the motion of the emitter. In one stage of this architecture, particle swarm optimization is used to simultaneously estimate the environment and the emitter location. In another stage, a Hough transform-inspired boundary localization algorithm is extended to 3D settings, to establish an initial estimate of the environment. The performance of this holistic approach is analyzed and its reliability is demonstrated in a reverberant watertank testbed, which models the shallow-water underwater acoustic setting.

Model-data comparison of sound propagation in a glacierized fjord with a simulated brash ice surface.

Glacier ice loss impacts sound propagation within Arctic fjords. Regular calving events contribute to a collection of floating ice fragments, known as brash ice, at the ocean surface that obstruct the natural and anthropogenic acoustic signals, yet are difficult to characterize. Transmission loss measurements using a maximum length sequence (m-sequence) signal were conducted in September 2017 near Hansbreen glacier in Hornsund Fjord, Svalbard with dense brash ice present at the water surface. An acoustic model of the brash ice surface was inferred through consideration of the experimental geometry, arrival amplitude, and travel time difference between the direct and surface reflected arrivals from the source to two receivers. The inferred surface was then incorporated into a forward simulation of the environment using sound speed profiles measured during the experiment. BELLHOP ([Porter and Bucker (1987). J. Acoust. Soc. Am. 82(4), 1349-1359],), a ray tracing code available in the Acoustics Toolbox (HLS Inc., San Diego, CA), was used to track the time difference of arrivals and amplitudes of the modeled direct and surface reflected rays. Comparisons between the measured and simulated results provide insight into the geometric shape and reflection characteristics of the brash ice surface within this and similar environments.

A numerical simulation framework for bubbly flow and sound generation in laboratory-scale breaking waves.

A simulation framework for bubbly flow and the sound radiated by breaking waves is presented. It consists of a two-phase flow solver, an algorithm to track bubbles and bubble creation rates, and a module to compute the sound generated by newly-formed bubbles. The sounds from breaking, third-order Stokes waves of 0.25 m wavelength and two slopes are calculated. The results show encouraging agreement with existing laboratory observations and identify the importance of air cylinder breakup in bubble creation. Remaining problems include modeling boundary effects that inhibit bubble coalescence in seawater and the generation of sound by the breakup of air cylinders.

Vertical directionality and spatial coherence of the sound field in glacial bays in Hornsund Fjord.

Arctic glacial bays are among the loudest natural environments in the ocean, owing to heavy submarine melting, calving, freshwater discharge, and ice-wave interactions. Understanding the coherence and vertical directionality of the ambient sound there can provide insights about the mechanisms behind the ice loss in these regions. It can also provide key information for operating technologies such as sonar, communication, and navigation systems. To study the unexplored sound coherence and vertical directionality in glacial bays, a vertical hydrophone array was deployed, and acoustic measurements were made at four glacier termini in Hornsund Fjord, Spitsbergen, in June and July 2019. The measurements show that the sound generated by melting glacier ice is more dominant in the upper portion of the water column near the glacier terminus. The melt water from the submarine melting and the freshwater discharge from the glacier create a glacially modified water duct near the sea surface. This disrupts the inter-sensor vertical coherence in the channel. However, some coherence across the duct is preserved for sound arising from spatially localized events at low frequencies. Overall, the observations in this study can help improve the understanding of the submarine melting phenomenon in glacial bays.

The role of jet and film drops in controlling the mixing state of submicron sea spray aerosol particles.

The oceans represent a significant global source of atmospheric aerosols. Sea spray aerosol (SSA) particles comprise sea salts and organic species in varying proportions. In addition to size, the overall composition of SSA particles determines how effectively they can form cloud droplets and ice crystals. Thus, understanding the factors controlling SSA composition is critical to predicting aerosol impacts on clouds and climate. It is often assumed that submicrometer SSAs are mainly formed by film drops produced from bursting bubble-cap films, which become enriched with hydrophobic organic species contained within the sea surface microlayer. In contrast, jet drops formed from the base of bursting bubbles are postulated to mainly produce larger supermicrometer particles from bulk seawater, which comprises largely salts and water-soluble organic species. However, here we demonstrate that jet drops produce up to 43% of total submicrometer SSA number concentrations, and that the fraction of SSA produced by jet drops can be modulated by marine biological activity. We show that the chemical composition, organic volume fraction, and ice nucleating ability of submicrometer particles from jet drops differ from those formed from film drops. Thus, the chemical composition of a substantial fraction of submicrometer particles will not be controlled by the composition of the sea surface microlayer, a major assumption in previous studies. This finding has significant ramifications for understanding the factors controlling the mixing state of submicrometer SSA particles and must be taken into consideration when predicting SSA impacts on clouds and climate.

Determination of ocean surface wave shape from forward scattered sound.

Forward scattered sound from the ocean surface is inverted for wave shape during three periods: low wind, mix of wind and swell, and stormy. Derived wave profiles are spatially limited to a Fresnel region at or near the nominal surface specular reflection point. In some cases, the surface wave profiles exhibit unrealistic temporal and spatial properties. To remedy this, the spatial gradient of inverted waves is constrained to a maximum slope of 0.88. Under this global constraint, only surface waves during low wind conditions result in a modeled surface multipath that accurately matches data. The power spectral density of the inverted surface wave field saturates around a frequency of 8 Hz while upward looking SONAR saturates at 1 Hz. Each shows a high frequency spectral slope of -4 that is in agreement with various empirical ocean wave spectra. The improved high frequency resolution provided by the scattering inversion indicates that it is possible to remotely gain information about high frequency components of ocean waves. The inability of the inversion algorithm to determine physically realistic surface waves in periods of high wind indicates that bubbles and out of plane scattering become important in those operating scenarios.

Intensity statistics of very high frequency sound scattered from wind-driven waves.

The interaction of vhf 100-1000 kHz underwater sound with the ocean surface is explored. The bistatic forward scatter of 300 kHz sound is measured in a wind driven wave channel. Fluctuations in arrival amplitude are described by the scintillation index (SI) which is a measure of arrival intensity variance. SI initially increases with wind speed but eventually saturates to a value of 0.5 when the root-mean-square (rms) roughness is 0.5 mm. An adjusted scintillation index (SI*) is suggested that accounts for the multiple arrivals and properly saturates to a value of 1. Fluctuations in arrival time do not saturate and increase proportionately to the dominant surface wave component. Forward scattering is modeled at frequencies ranging from 50 to 2000 kHz using the Helmholtz-Kirchhoff integral with surface wave realizations derived from wave gauge data. The amplitude and temporal statistics of the simulated scattering agree well with measured data. Intensity saturation occurs at lower wind speeds for higher frequency sound. Both measured and modeled vhf sound is characterized by many surface arrivals at saturation. Doppler shifts associated with wave motion are expected to vary rapidly for vhf sound however further analysis is required.

Sea Spray Aerosol Structure and Composition Using Cryogenic Transmission Electron Microscopy.

The composition and surface properties of atmospheric aerosol particles largely control their impact on climate by affecting their ability to uptake water, react heterogeneously, and nucleate ice in clouds. However, in the vacuum of a conventional electron microscope, the native surface and internal structure often undergo physicochemical rearrangement resulting in surfaces that are quite different from their atmospheric configurations. Herein, we report the development of cryogenic transmission electron microscopy where laboratory generated sea spray aerosol particles are flash frozen in their native state with iterative and controlled thermal and/or pressure exposures and then probed by electron microscopy. This unique approach allows for the detection of not only mixed salts, but also soft materials including whole hydrated bacteria, diatoms, virus particles, marine vesicles, as well as gel networks within hydrated salt droplets-all of which will have distinct biological, chemical, and physical processes. We anticipate this method will open up a new avenue of analysis for aerosol particles, not only for ocean-derived aerosols, but for those produced from other sources where there is interest in the transfer of organic or biological species from the biosphere to the atmosphere.

Sea spray aerosol as a unique source of ice nucleating particles.

Ice nucleating particles (INPs) are vital for ice initiation in, and precipitation from, mixed-phase clouds. A source of INPs from oceans within sea spray aerosol (SSA) emissions has been suggested in previous studies but remained unconfirmed. Here, we show that INPs are emitted using real wave breaking in a laboratory flume to produce SSA. The number concentrations of INPs from laboratory-generated SSA, when normalized to typical total aerosol number concentrations in the marine boundary layer, agree well with measurements from diverse regions over the oceans. Data in the present study are also in accord with previously published INP measurements made over remote ocean regions. INP number concentrations active within liquid water droplets increase exponentially in number with a decrease in temperature below 0 °C, averaging an order of magnitude increase per 5 °C interval. The plausibility of a strong increase in SSA INP emissions in association with phytoplankton blooms is also shown in laboratory simulations. Nevertheless, INP number concentrations, or active site densities approximated using "dry" geometric SSA surface areas, are a few orders of magnitude lower than corresponding concentrations or site densities in the surface boundary layer over continental regions. These findings have important implications for cloud radiative forcing and precipitation within low-level and midlevel marine clouds unaffected by continental INP sources, such as may occur over the Southern Ocean.

Bubble stimulation efficiency of dinoflagellate bioluminescence.

Dinoflagellate bioluminescence, a common source of bioluminescence in coastal waters, is stimulated by flow agitation. Although bubbles are anecdotally known to be stimulatory, the process has never been experimentally investigated. This study quantified the flash response of the bioluminescent dinoflagellate Lingulodinium polyedrum to stimulation by bubbles rising through still seawater. Cells were stimulated by isolated bubbles of 0.3-3 mm radii rising at their terminal velocity, and also by bubble clouds containing bubbles of 0.06-10 mm radii for different air flow rates. Stimulation efficiency, the proportion of cells producing a flash within the volume of water swept out by a rising bubble, decreased with decreasing bubble radius for radii less than approximately 1 mm. Bubbles smaller than a critical radius in the range 0.275-0.325 mm did not stimulate a flash response. The fraction of cells stimulated by bubble clouds was proportional to the volume of air in the bubble cloud, with lower stimulation levels observed for clouds with smaller bubbles. An empirical model for bubble cloud stimulation based on the isolated bubble observations successfully reproduced the observed stimulation by bubble clouds for low air flow rates. High air flow rates stimulated more light emission than expected, presumably because of additional fluid shear stress associated with collective buoyancy effects generated by the high air fraction bubble cloud. These results are relevant to bioluminescence stimulation by bubbles in two-phase flows, such as in ship wakes, breaking waves, and sparged bioreactors.

Advancing Model Systems for Fundamental Laboratory Studies of Sea Spray Aerosol Using the Microbial Loop.

Sea spray aerosol (SSA) particles represent one of the most abundant surfaces available for heterogeneous reactions to occur upon and thus profoundly alter the composition of the troposphere. In an effort to better understand tropospheric heterogeneous reaction processes, fundamental laboratory studies must be able to accurately reproduce the chemical complexity of SSA. Here we describe a new approach that uses microbial processes to control the composition of seawater and SSA particle composition. By inducing a phytoplankton bloom, we are able to create dynamic ecosystem interactions between marine microorganisms, which serve to alter the organic mixtures present in seawater. Using this controlled approach, changes in seawater composition become reflected in the chemical composition of SSA particles 4 to 10 d after the peak in chlorophyll-a. This approach for producing and varying the chemical complexity of a dominant tropospheric aerosol provides the foundation for further investigations of the physical and chemical properties of realistic SSA particles under controlled conditions.

Directionality of the ambient noise field in an Arctic, glacial bay.

The directionality of ambient noise in an Arctic tidewater glacier bay was measured using two horizontally spaced, broadband hydrophones. Segments of noise were divided into two frequency bands and analyzed for arrival angle. These data show that different classes of source radiate noise in distinct spectral bands and are spatially diverse. A previously unidentified source, the interaction of surface gravity waves with underside of ice ledges at the periphery of icebergs, is described. The generation of noise by ice-wave interaction suggests that surface waves should be measured if ambient noise is to be used to monitor ice dynamics in glacial fjords.

Reconstructing surface wave profiles from reflected acoustic pulses using multiple receivers.

Surface wave shapes are determined by analyzing underwater reflected acoustic signals collected at multiple receivers. The transmitted signals are of nominal frequency 300 kHz and are reflected off surface gravity waves that are paddle-generated in a wave tank. An inverse processing algorithm reconstructs 50 surface wave shapes over a length span of 2.10 m. The inverse scheme uses a broadband forward scattering model based on Kirchhoff's diffraction formula to determine wave shapes. The surface reconstruction algorithm is self-starting in that source and receiver geometry and initial estimates of wave shape are determined from the same acoustic signals used in the inverse processing. A high speed camera provides ground-truth measurements of the surface wave field for comparison with the acoustically derived surface waves. Within Fresnel zone regions the statistical confidence of the inversely optimized surface profile exceeds that of the camera profile. Reconstructed surfaces are accurate to a resolution of about a quarter-wavelength of the acoustic pulse only within Fresnel zones associated with each source and receiver pair. Multiple isolated Fresnel zones from multiple receivers extend the spatial extent of accurate surface reconstruction while overlapping Fresnel zones increase confidence in the optimized profiles there.

Reconstructing surface wave profiles from reflected acoustic pulses.

Surface wave shapes are determined by analyzing underwater reflected acoustic signals. The acoustic signals (of nominal frequency 200 kHz) are forward scattered from the underside of surface waves that are generated in a wave tank and scaled to model smooth ocean swell. An inverse processing algorithm is designed and implemented to reconstruct the surface displacement profiles of the waves over one complete period. The inverse processing uses the surface scattered pulses collected at the receiver, an initial wave profile (two are considered), and a broadband forward scattering model based on Kirchhoff's diffraction formula to iteratively adjust the surface until it is considered optimized or reconstructed. Two physical length scales over which information can be known about the surface are confirmed. An outer length scale, the Fresnel zone surrounding each specular reflection point, is the only region where optimized surfaces resulting from each initial profile converge within a resolution set by the inner length scale, a quarter-wavelength of the acoustic pulse. The statistical confidence of each optimized surface is also highest within a Fresnel zone. Future design considerations are suggested such as an array of receivers that increases the region of surface reconstruction by a factor of 2 to 3.

Bringing the ocean into the laboratory to probe the chemical complexity of sea spray aerosol.

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.

Determining the bubble cap film thickness of bursting bubbles from their acoustic emissions.

A study of the sound generated by 2.5 mm radius bubbles bursting on the surface of fresh water is presented. The sound pulses are found to be sensitive to the time interval between the bubble reaching the water surface and bursting. Bubbles that burst within a few 10's of milliseconds behave like a Helmholtz resonator and radiate a swept chirp pulse. Bubbles that persist for 100's of milliseconds or more exhibit more complex acoustic behavior. An analysis of the resonator behavior provides an estimate of the film thickness in reasonable agreement with a fluid drainage model.