Ocean emission of microplastic.

Microplastics are globally ubiquitous in marine environments, and their concentration is expected to continue rising at significant rates as a result of human activity. They present a major ecological problem with well-documented environmental harm. Sea spray from bubble bursting can transport salt and biological material from the ocean into the atmosphere, and there is a need to quantify the amount of microplastic that can be emitted from the ocean by this mechanism. We present a mechanistic study of bursting bubbles transporting microplastics. We demonstrate and quantify that jet drops are efficient at emitting microplastics up to 280µm in diameter and are thus expected to dominate the emitted mass of microplastic. The results are integrated to provide a global microplastic emission model which depends on bubble scavenging and bursting physics; local wind and sea state; and oceanic microplastic concentration. We test multiple possible microplastic concentration maps to find annual emissions ranging from 0.02 to 7.4-with a best guess of 0.1-mega metric tons per year and demonstrate that while we significantly reduce the uncertainty associated with the bursting physics, the limited knowledge and measurements on the mass concentration and size distribution of microplastic at the ocean surface leaves large uncertainties on the amount of microplastic ejected.

Highly efficient preconcentration using anodically generated shrinking gas bubbles for per- and polyfluoroalkyl substances (PFAS) detection.

Here we report a highly efficient PFAS preconcentration method that uses anodically generated shrinking gas bubbles to preconcentrate PFAS via aerosol formation, achieving ~ 1400-fold enrichment of PFOS and PFOA-the two most common PFAS-in 20 min. This new method improves the enrichment factor by 15 to 105% relative to the previous method that uses cathodically generated H2 bubbles. The shrinking gas bubbles are in situ electrogenerated by oxidizing water in an NH4HCO3 solution. H+ produced by water oxidation reacts with HCO3- to generate CO2 gas, forming gas bubbles containing a mixture of O2 and CO2. Due to the high solubility of CO2 in aqueous solutions, the CO2/O2 bubbles start shrinking when they leave the electrode surface region. A mechanistic study reveals two reasons for the improvement: (1) shrinking bubbles increase the enrichment rate, and (2) the attractive interactions between the positively charged anode and negatively charged PFAS provide high enrichment at zero bubble path length. Based on this preconcentration method, we demonstrate the detection of ≥ 70 ng/L PFOA and PFOS in water in ~ 20 min by coupling it with our bubble-nucleation-based detection method, fulfilling the need of the US Environmental Protection Agency.

New insights into the role of marine plastic-gels in microplastic transfer from water to the atmosphere via bubble bursting.

The pervasiveness of microplastics (MPs) in global oceans is raising concerns about their adverse impacts on ecosystems. The mechanistic understanding of MP transport is critical for evaluating its fate, flux, and ecological risks specifically. Currently, bubble bursting is believed to represent an important route for MP transfer from sea surfaces to the atmosphere. However, the detailed mechanisms of the complex physico-chemical interactions between MPs, water composition, and gel particles in the air-sea interface remain unknown. Our results suggested three steps for MP transfer between air-sea phases: (1) MPs incorporating into gel aggregates in the water column; (2) further accumulation of plastic-gel aggregate in the surface layer phase; finally (3) ejection of aggregates from the sea when bubbles of trapped air rise to the surface and burst. The water composition (e.g., high salinity, gel concentration and viscosity) can modulate plastic-gel aggregation and subsequent transport from water to the atmosphere. The possible mechanism may be closely tied to the formation of plastic-gel via cation-linking bridges, thereby enhancing plastic-gel ejection into air. Collectively, this work offers unique insights into the role of marine plastic-gels in determining MP fate and transport, especially at air-sea interfaces. The data also provide a better understanding of the corresponding mechanism that may explain the fates of missing plastics in the ocean.

Water-to-Air Transfer of Nano/Microsized Particulates: Enrichment Effect in Bubble Bursting Jet Drops.

Bubbles dispersed in liquids are widely present in many natural and industrial processes and play a key role in mediating mass transfer during their lifetime from formation to rising to bursting. In particular, nano/microsized particulates and organisms present in the bulk water can be highly enriched in the jet drops ejected during bubble bursting, impacting global climate and public health. However, the detailed mechanism of this enrichment remains obscure with the enrichment factor being difficult to predict. Here, we experimentally investigate the enrichment of nano/microsized particles in bubble bursting jet drops and highlight the underlying hydrodynamic mechanism, combining the effects of bubble scavenge and bursting on the transport of particles. Scaling laws for the enrichment factor are subsequently proposed that describe both our and prior experimental results reasonably well. Our study may provide new insights for water-to-air transfer of bulk particulates such as microbes related to bubble bursting.

Optimisation on the Performance of Bubble-Bursting Atomisation for Minimum Quantity Lubrication with Vegetable Oil Using Computational Fluid Dynamics Simulation.

Sustainable and green machining technologies have become a welcomed topic in the manufacturing industries. One of the emerging sustainable technologies is minimum quantity lubrication (MQL). In this study, the optimisation and study of the bubble-bursting atomisation system applied to MQL machining is carried out through the computational fluid dynamics (CFD) simulation approach. Vegetable oil is selected as the cooling lubricant in this study. The performance of the bubble-bursting atomisation system is improved by alternating air inlet velocity and the gap distance between the inlets of bubble production. A velocity of 0.1 ms-1 is suitable for the air at the inlets for the bubble production, whereas 10 ms-1 is suitable for the velocity of the air at the inlet, where the droplets of vegetable oil are guided to the nozzle. Besides that, a 50 mm gap distance between the air inlets for the production of bubbles is able to avoid the occurrence of bubble coalescence. Under these conditions, optimal bubble sizes of 2-3 mm can be achieved, with a higher probability of nano-sized droplets being present in these ranges. Furthermore, a higher rate and smaller size of vegetable oil droplets escaping the atomisation chamber and reaching the machining zone will be generated. Thus, the performance of the MQL machining can be improved.

Bubbles spray aerosols: Certitudes and mysteries.

Ocean spray aerosol formed by bubble bursting are at the core of a broad range of atmospheric processes: they are efficient cloud condensation nuclei and carry a variety of chemical, biological, and biomass material from the surface of the ocean to the atmosphere. The origin and composition of these aerosols is sensibly controlled by the detailed fluid mechanics of bubble bursting. This perspective summarizes our present-day knowledge on how bursting bubbles at the surface of a liquid pool contribute to its fragmentation, namely to the formation of droplets stripped from the pool, and associated mechanisms. In particular, we describe bounds and yields for each distinct mechanism, and the way they are sensitive to the bubble production and environmental conditions. We also underline the consequences of each mechanism on some of the many air-sea interactions phenomena identified to date. Attention is specifically payed at delimiting the known from the unknown and the certitudes from the speculations.

Ultrafast Bubble Bursting by Superamphiphobic Coatings.

Controlling bubble motion or passively bursting bubbles using solid interfaces is advantageous in numerous industrial applications including flotation, catalysis, electrochemical processes, and microfluidics. Current research has explored the formation, dissolution, pinning, and rupturing of bubbles on different surfaces. However, the ability to tune and control the rate of bubble bursting is not yet achieved. Scaling down surface-induced bubble bursting to just a few milliseconds is important for any application. In this work, the hierarchical structure of superamphiphobic surfaces is tuned in order to rapidly rupture contacting bubbles. Surfaces prepared using liquid flame spray show ultrafast bubble bursting (down to 2 ms) and superior durability. The coatings demonstrate excellent mechanical and chemical stability even in the presence of surface-active species. Air from the ruptured bubble is absorbed into the aerophilic Cassie-state. Long-term applicability is demonstrated by preventing the accumulation of air in the plastron via a connection of the plastron to the environment. The times recorded for bubble rupture and complete reorganization of air are reduced by approximately a factor of 3 compared to previously reported values. The concept is utilized to passively control surfactant-rich foam in froth flotation. Material collection efficiency increased by more than 60 times compared to controls.

Experimental evidence of plastic particles transfer at the water-air interface through bubble bursting.

Plastic debris in the marine environment are the subject of an extensive literature. According to studies dedicated to the determination of plastic litter abundance and to the characterisation of degradation and fragmentation processes, models were used to estimate the global plastic debris abundance and to simulate their transfer and distribution. Despite these efforts, there is still missing plastic in the models used as areas exist where plastic abundance is less than that estimated. In parallel, microplastics presence in the atmosphere and in remote areas was confirmed suggesting long range atmospheric transport. Potentially addressing both these issues, recent literature suggests that microplastics (MPs) and nanoplastics (NPs) can be transferred from the marine environment to the atmosphere via the bursting of air bubbles at the sea surface. Nevertheless, to date there is no direct evidence of this transfer. In this study, we evaluate plastic particles transfer as a function of MPs/NPs characteristics and water composition by simulating the bubble bursting phenomenon in a laboratory reactor. Size distribution of transferred particles were recorded, and their plastic nature was confirmed using electron microscopy. Results show that under tested conditions, the transfer is possible but limited to particles smaller than 1 µm. The influence of the presence of proxies of components of the sea surface microlayer in the water was evaluated showing a higher particle transfer rate in the presence of a surfactant (sodium dodecyl sulfate) and no significant effect of polysaccharides (xanthan gum and dextran). The surface state of the particles can alter their behaviour in the aqueous phase and thus their transfer to the atmosphere. The effect of bubble size was also evaluated showing a higher transfer rate with the smaller bubble size. In addition, experiments performed with grounded polyethylene (PE) samples showed higher transfer for UV-aged PE than for pristine PE.

A bubble bursting-mediated oral drug delivery system that enables concurrent delivery of lipophilic and hydrophilic chemotherapeutics for treating pancreatic tumors in rats.

The therapeutic outcome of pancreatic cancer remains unsatisfactory, despite many attempts to improve it. To address this challenge, an oral drug delivery system that spontaneously initiates an effervescent reaction to form gas-bubble carriers is proposed. These carriers concurrently deliver lipophilic paclitaxel (PTX) and hydrophilic gemcitabine (GEM) in the small intestine. The bursting of the bubbles promotes the intestinal absorption of the drugs. The antitumor efficacy of this proposed oral drug delivery system is evaluated in rats with experimentally created orthotopic pancreatic tumors. The combined administration of equivalent amounts of PTX and GEM via the intravenous (i.v.) route, which is clinically used for treating pancreatic cancer, serves as a control. Following oral administration, the lipophilic PTX is initially absorbed through the intestinal lymphatic system and then enters systemic circulation, whereas the hydrophilic GEM is directly taken up into the blood circulation, ultimately accumulating in the tumorous pancreatic tissues. A pharmacokinetic study reveals that the orally delivered formulation has none of the toxic side-effects that are associated with the i.v. injected formulation; changes the pharmacokinetic profiles of the drugs; and increases the bioavailability of PTX. The oral formulation has a greater impact than the i.v. formulation on tumor-specific stromal depletion, resulting in greater inhibition of tumor growth with no evidence of metastatic spread. As well as enhancing the therapeutic efficacy, this unique approach of oral chemotherapy has potential for use on outpatients, greatly improving their quality of life.

Impact of dispersant on crude oil content of airborne fine particulate matter emitted from seawater after an oil spill.

Inhalation of PM2.5, particles with an aerodynamic diameter <2.5 µm, from sea spray after crude oil spills could present serious health concerns. The addition of dispersants to effectively spread the crude oil throughout the water column has been practiced in recent years. Here, we investigated the possibility of an increase in the toxic content of fine PM after adding dispersant. A laboratory setup consisted of a vertical tank filled with seawater, 31.5 L airspace for aerosol sampling, and a bubble generating nozzle that aerosolized the oily droplets. Four different cases were studied: no slick, 0.5-mm-thick slick of pure crude oil (MC252 surrogate), dispersant (Corexit 9500A) mixed with crude oil at dispersant to oil ratio (DOR) 1:25, and DOR 1:100. The resulting airborne droplets were sampled for gravimetric and chemical analyses through development of a gas chromatography and mass spectrometry technique. Also, PM2.5 particles were size-fractioned into 13 size bins covering <60 nm to 12.1 µm using a low-pressure cascade impactor. The highest PM2.5 concentration (20.83 ± 5.21 µg/m3) was released from a slick of DOR 1:25, 8.83× greater than the case with pure crude oil. The average ratio of crude oil content from the slick of DOR 1:25 to the case with pure crude oil was 2.37 (1.83 vs 0.77 µg/m3) that decreased to 1.17 (0.90 vs 0.77 µg/m3) at DOR 1:100. For particles <220 nm, the resultant crude oil concentrations were 0.64 and 0.29 µg/m3 at DOR 1:25 and 1:100, both higher than 0.11 µg/m3 from the slick of pure crude oil.

Corrigendum: Effect of Aerosolization and Drying on the Viability of Pseudomonas syringae Cells.

[This corrects the article DOI: 10.3389/fmicb.2018.03086.].

Air bubble bursting phenomenon at the air-water interface monitored by the piezoelectric-acoustic method.

When an air bubble arrives at the free interface, the bubble's lamella drains and ruptures. The bubble collapses, and gas vapor is released. The ruptured lamella retreats, and a rim at the edge of the retreating lamella forms. The rim becomes unstable and breaks into fine droplets, leading to the formation of a mist. As the collapsing bubble gas's vapor is released, the collapsing bubble oscillates and a vertical liquid jet erupts; this jet then breaks into a droplet(s). Here, we present a novel approach for monitoring the air bubble bursting frequency at the air-water interface by the piezoelectric-pressure-acoustic technique. The piezoelectric-acoustic technique monitors the lamella's rupture time, the frequency of the oscillation of the collapsing air bubble, and the frequency of the oscillation at the free air/water interface. The aqueous lamella rupture thickness was probed by reflected light interferometry, and the air bubble burst at the air/water interface was monitored with the high-speed photo imaging technique. The data obtained by the three techniques provided essential information for the stages of the air bubble collapse dynamics at the free interface without the presence of a surfactant. The simple model proposed by Rayleigh, Minnaert, and Lighthill (RML) for the oscillation resonance of a single air bubble was applied to calculate the air bubble collapsing frequency. The floating air bubble bursting frequency with an equatorial radius of 0.33 ±â€¯0.05 cm was well predicted using the air bubble resonance frequency model, and was estimated as 1.0 ±â€¯0.3 kHz. The velocity of the ruptured aqueous lamella covering the air bubble was estimated as 1 m/s. This research presents a comprehensive understanding of the phenomenon of the bare air bubble collapse at the free interface.

Wind-driven spume droplet production and the transport of Pseudomonas syringae from aquatic environments.

Natural aquatic environments such as oceans, lakes, and rivers are home to a tremendous diversity of microorganisms. Some may cross the air-water interface within droplets and become airborne, with the potential to impact the Earth's radiation budget, precipitation processes, and spread of disease. Larger droplets are likely to return to the water or adjacent land, but smaller droplets may be suspended in the atmosphere for transport over long distances. Here, we report on a series of controlled laboratory experiments to quantify wind-driven droplet production from a freshwater source for low wind speeds. The rate of droplet production increased quadratically with wind speed above a critical value (10-m equivalent 5.7 m/s) where droplet production initiated. Droplet diameter and ejection speeds were fit by a gamma distribution. The droplet mass flux and momentum flux increased with wind speed. Two mechanisms of droplet production, bubble bursting and fragmentation, yielded different distributions for diameter, speed, and angle. At a wind speed of about 3.5 m/s, aqueous suspensions of the ice-nucleating bacterium Pseudomonas syringae were collected at rates of 283 cells m-2 s-1 at 5 cm above the water surface, and at 14 cells m-2 s-1 at 10 cm above the water surface. At a wind speed of about 4.0 m/s, aqueous suspensions of P. syringae were collected at rates of 509 cells m-2 s-1 at 5 cm above the water surface, and at 81 cells m-2 s-1 at 10 cm above the water surface. The potential for microbial flux into the atmosphere from aquatic environments was calculated using known concentrations of bacteria in natural freshwater systems. Up to 3.1 × 104 cells m-2 s-1 of water surface were estimated to leave the water in potentially suspended droplets (diameters <100 µm). Understanding the sources and mechanisms for bacteria to aerosolize from freshwater aquatic sources may aid in designing management strategies for pathogenic bacteria, and could shed light on how bacteria are involved in mesoscale atmospheric processes.

Plug-and-Play Nanorization of Coarse Black Phosphorus for Targeted Chemo-photoimmunotherapy of Colorectal Cancer.

Because of their extraordinary physical properties and biocompatibility, black phosphorus (BP) nanosheets (NSs) have been intensively employed in chemo-phototherapies, such as plasmonic inorganic nanoparticles or graphene NSs, over the past few years. However, most biomedical studies using BP NSs are only concerned with the optical property of BP NSs to repeatedly demonstrate chemo-phototherapeutic efficacies, although BP NSs have different properties from inorganic nanoparticles or graphene NSs, such as corrugated crystal structure, hydrophilicity, and biodegradability. Moreover, it is still a challenging issue to efficiently fabricate uniform BP NSs for clinical translation because of the top-down nature of fabrication, despite the easy preparation of coarse BP flakes. It is thus essential to explore their most suitable bioapplications as well as suggest an easy-to-access strategy to produce uniform BP NSs for realization as advanced therapeutic materials. To rationalize these issues, this report introduces a plug-and-play nanorization, ultrasonic bubble bursting, of coarse BP flakes for continuous BP NS production, and the resulting uniform NSs (∼40 nm lateral dimension, ∼0.15 polydispersity index) were used as base materials to load drug (doxorubicin), targeting agent (chitosan-polyethylene glycol), and cancer growth inhibitor (programmed death ligand 1 and small interfering RNA) for achieving efficacious chemo-photoimmunotherapy of colorectal cancer.

Effect of Aerosolization and Drying on the Viability of Pseudomonas syringae Cells.

Airborne dispersal of microorganisms influences their biogeography, gene flow, atmospheric processes, human health and transmission of pathogens that affect humans, plants and animals. The extent of their impact depends essentially on cell-survival rates during the process of aerosolization. A central factor for cell-survival is water availability prior to and upon aerosolization. Also, the ability of cells to successfully cope with stress induced by drying determines their chances of survival. In this study, we used the ice-nucleation active, plant pathogenic Pseudomonas syringae strain R10.79 as a model organism to investigate the effect of drying on cell survival. Two forms of drying were simulated: drying of cells in small droplets aerosolized from a wet environment by bubble bursting and drying of cells in large droplets deposited on a surface. For drying of cells both in aerosol and surface droplets, the relative humidity (RH) was varied in the range between 10 and 90%. The fraction of surviving cells was determined by live/dead staining followed by flow cytometry. We also evaluated the effect of salt concentration in the water droplets on the survival of drying cells by varying the ionic strength between 0 and 700 mM using NaCl and sea salt. For both aerosol and surface drying, cell survival increased with decreasing RH (p < 0.01), and for surface drying, survival was correlated with increasing salt concentration (p < 0.001). Imaging cells with TEM showed shrunk cytoplasm and cell wall damage for a large fraction of aerosolized cells. Ultimately, we observed a 10-fold higher fraction of surviving cells when dried as aerosol compared to when dried on a surface. We conclude that the conditions, under which cells dry, significantly affect their survival and thus their success to spread through the atmosphere and colonize new environments as well as their ability to affect atmospheric processes.

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.