The mass flux at the surface of a drop in an immiscible host liquid is dictated by the composition of the drop surface. In a binary system, this composition is essentially constant in time and equals the solubility of the drop constituent in the host liquid. This situation has been treated in a classic study by Epstein and Plesset (J. Chem. Phys., vol. 18, 1950, pp. 1505–1509). The situation is very different for ternary and higher-order systems in which, due to the mutual interaction of the drop constituents, their concentration at the drop surface markedly differs from the respective solubilities and depends on time. This paper presents a thermodynamically consistent analysis of this situation, for both growing and dissolving drops, with and without an initial concentration of the drop constituents in the host liquid. In some cases the results, which have important implications e.g. for solvent extraction processes in the chemical and environmental remediation industries, show major deviations from the predictions of approximations in current use, including simple extensions of the Epstein–Plesset theory.

This note examines the modeling of non-convective fluxes (e.g., stress, heat flux and others) as they appear in the general, unclosed form of the volume-averaged equations of multiphase flows. By appealing to the difference between slowly and rapidly varying quantities, it is shown that the natural closure of these terms leads to the use of a single, slowly-varying combined average flux, common to both phases, plus rapidly-varying local contributions for each phase. The result is general and only rests on the hypothesis that the spatial variation of the combined average flux is adequately described by a linear function of position within the averaging volume. No further hypotheses on the nature of the flow (e.g., about specific flow regimes) prove necessary. The result agrees with earlier ones obtained by ensemble averaging, is illustrated with the example of disperse flows and discussed in the light of some earlier and current literature. A very concise derivation of the general averaged balance equation is also given.

We conducted a large scale experiment of underwater oil release of 6.3 L/s through a 25.4 mm (one inch) horizontal pipe. Detailed measurements of plume trajectory, velocity, oil droplet size distribution, and oil holdup were obtained. The obtained experimental data were used for the validation of the models JETLAG and VDROP-J. Key findings include: (1) formation of two plumes, one due to momentum and subsequently plume buoyancy, and another due mostly to the buoyancy of individual oil droplets that separate upward from the first plume; (2) modeling results indicated that the traditional miscible plume models matched the momentum and buoyancy plume, but were not able to simulate the upward motion plume induced by individual oil droplets; (3) high resolution images in the jet primary breakup region showed the formation of ligaments and drops in a process known as “primary breakup”. These threads re-entered the plume to re-break in a process known as “secondary breakup”; (4) the plume velocity was highly heterogeneous with regions of high velocity surrounded by stagnant regions for various durations. The results from this study revealed that the primary breakup is a key factor for quantifying the droplet size distribution which plays a crucial role in determining the ultimate fate and transport of the released oil in the marine environment. The observed spatial heterogeneity in the oil plume implies that the effectiveness of applied dispersants may vary greatly when applying directly in the discharged oil flow.

Toxic effects of petroleum to marine zooplankton have been generally investigated using dissolved petroleum hydrocarbons and in the absence of sunlight. In this study, we determined the influence of natural ultraviolet B (UVB) radiation on the lethal and sublethal toxicity of dispersed crude oil to naupliar stages of the planktonic copepodsAcartia tonsa, Temora turbinata and Pseudodiaptomus pelagicus. Low concentrations of dispersed crude oil (1 μL L⁻¹) caused a significant reduction in survival, growth and swimming activity of copepod nauplii after 48 h of exposure. UVB radiation increased toxicity of dispersed crude oil by 1.3–3.8 times, depending on the experiment and measured variables. Ingestion of crude oil droplets may increase photoenhanced toxicity of crude oil to copepod nauplii by enhancing photosensitization. Photoenhanced sublethal toxicity was significantly higher when T. turbinata nauplii were exposed to dispersant-treated oil than crude oil alone, suggesting that chemical dispersion of crude oil may promote photoenhanced toxicity to marine zooplankton. Our results demonstrate that acute exposure to concentrations of dispersed crude oil and dispersant (Corexit 9500) commonly found in the sea after oil spills are highly toxic to copepod nauplii and that natural levels of UVB radiation substantially increase the toxicity of crude oil to these planktonic organisms. Overall, this study emphasizes the importance of considering sunlight in petroleum toxicological studies and models to better estimate the impact of crude oil spills on marine zooplankton.

Oil–particle interactions play a major role in removal of free oil from the water column. We present a new conceptual–numerical model, A-DROP, to predict oil amount trapped in oil–particle aggregates. A new conceptual formulation of oil–particle coagulation efficiency is introduced to account for the effects of oil stabilization by particles, particle hydrophobicity, and oil–particle size ratio on OPA formation. A-DROP was able to closely reproduce the oil trapping efficiency reported in experimental studies. The model was then used to simulate the OPA formation in a typical nearshore environment. Modeling results indicate that the increase of particle concentration in the swash zone would speed up the oil–particle interaction process; but the oil amount trapped in OPAs did not correspond to the increase of particle concentration. The developed A-DROP model could become an important tool in understanding the natural removal of oil and developing oil spill countermeasures by means of oil–particle aggregation.

Gas is often emanated from the sea bed during a subsea oil and gas blowout. The size of a gas bubble changes due to gas dissolution in the ambient water and expansion as a result of a decrease in water pressure during the rise. It is important to understand the fate and transport of gas bubbles for the purpose of environmental and safety concerns. In this paper, we used the numerical model, VDROP-J to simulate gas formation in jet/plume upon release, and dissolution and expansion while bubble rising during a relatively shallow subsea gas blowout. The model predictions were an excellent match to the experimental data. Then a gas dissolution and expansion module was included in the VDROP-J model to predict the fate and transport of methane bubbles rising due to a blowout through a 0.10 m vertical ori- fice. The numerical results indicated that gas bubbles would increase the mixing energy in released jets, especially at small distances and large distances from the orifice. This means that models that predict the bubble size distribution (BSD) should account for this additional mixing energy. It was also found that only bubbles of certain sizes would reach the water surfaces; small bubbles dissolve fast in the water column, while the size of the large bubbles decreases. This resulted in a BSD that was bimodal near the ori- fice, and then became unimodal.

We investigated and quantified defecation rates of crude oil by 3 species of marine planktonic copepods (Temora turbinata, Acartia tonsa, and Parvocalanus crassirostris) and a natural copepod assemblage after exposure to mechanically or chemically dispersed crude oil. Between 88 and 100% of the analyzed fecal pellets from three species of copepods and a natural copepod assemblage exposed for 48 h to physically or chemically dispersed light crude oil contained crude oil droplets. Crude oil droplets inside fecal pellets were smaller (median diameter: 2.4–3.5 μm) than droplets in the physically and chemically dispersed oil emulsions (median diameter: 6.6 and 8.0 μm, respectively). This suggests that copepods can reject large crude oil droplets or that crude oil droplets are broken into smaller oil droplets before or during ingestion. Depending on the species and experimental treatments, crude oil defecation rates ranged from 5.3 to 245 ng-oil copepod⁻¹ d⁻¹, which represent a mean weight-specific defecation rate of 0.026 μg-oil μg-C_copepod¹ d⁻¹. Considering a dispersed crude oil concentration commonly found in the water column after oil spills (1 μl L⁻¹) and copepod abundances in high productive coastal areas, copepods may defecate ∼1.3–2.6 mg-oil m⁻³ d⁻¹, which would represent ∼0.15%–0.30% of the total dispersed oil per day. Our results indicate that ingestion and subsequent defecation of crude oil by planktonic copepods has a small influence on the overall mass of oil spills in the short term, but may be quantitatively important in the flux of oil from surface water to sediments and in the transfer of low-solubility, toxic petroleum hydrocarbons into food webs after crude oil spills in the sea.

Knowledge of the droplet size distribution (DSD) from the Deepwater Horizon (DWH) blowout is an important step in predicting the fate and transport of the released oil. Due to the absence of measurements of the DSD from the DWH incident, we considered herein hypothetical scenarios of releases that explore the realistic parameter space using a thoroughly calibrated DSD model, VDROP-J, and we attempted to provide bounds on the range of droplet sizes from the DWH blowout within 200 m of the wellhead. The scenarios include conditions without and with the presence of dispersants, different dispersant treatment efficiencies, live oil and dead oil properties, and varying oil flow rate, gas flow rate, and orifice diameter. The results, especially for dispersant-treated oil, are very different from recent modeling studies in the literature.

Knowledge of the droplet size distribution (DSD) from the Deepwater Horizon (DWH) blowout is an important step in predicting the fate and transport of the released oil. Due to the absence of measurements of the DSD from the DWH incident, we considered herein hypothetical scenarios of releases that explore the realistic parameter space using a thoroughly calibrated DSD model, VDROP-J, and we attempted to provide bounds on the range of droplet sizes from the DWH blowout within 200 m of the wellhead. The scenarios include conditions without and with the presence of dispersants, different dispersant treatment efficiencies, live oil and dead oil properties, and varying oil flow rate, gas flow rate, and orifice diameter. The results, especially for dispersant-treated oil, are very different from recent modeling studies in the literature.

Following the Deepwater Horizon (DWH) spill in 2010, an enormous amount of oil was observed in the deep and surface waters of the northern Gulf of Mexico. Surface waters are characterized by intense sunlight and high temperature during summer. While the oil-degrading bacterial communities in the deep-sea plume have been widely investigated, the effect of natural sunlight on those in oil polluted surface waters remains unexplored to date. In this study, we incubated surface water from the DWH site with amendments of crude oil, Corexit dispersant, or both for 36 d under natural sunlight in the northern Gulf of Mexico. The bacterial community was analyzed over time for total abundance, density of alkane and polycyclic aromatic hydrocarbon degraders, and community composition via pyrosequencing. Our results showed that, for treatments with oil and/or Corexit, sunlight significantly reduced bacterial diversity and evenness and was a key driver of shifts in bacterial community structure. In samples containing oil or dispersant, sunlight greatly reduced abundance of the Cyanobacterium Synechococcus but increased the relative abundances of Alteromonas, Marinobacter, Labrenzia, Sandarakinotalea, Bartonella, and Halomonas. Dark samples with oil were represented by members of Thalassobius, Winogradskyella, Alcanivorax, Formosa, Pseudomonas, Eubacterium, Erythrobacter, Natronocella, and Coxiella. Both oil and Corexit inhibited the Candidatus Pelagibacter with or without sunlight exposure. For the first time, we demonstrated the effects of light in structuring microbial communities in water with oil and/or Corexit. Overall, our findings improve understanding of oil pollution in surface water, and provide unequivocal evidence that sunlight is a key factor in determining bacterial community composition and dynamics in oil polluted marine waters.

Statistical mechanics provides the link between microscopic properties of many-particle systems and macroscopic properties such as pressure and temperature. Observations of similar "microscopic" quantities exist for the motion of zooplankton, as well as many species of other social animals. Herein, we propose to take average squared velocities as the definition of the "ecological temperature" of a population under different conditions on nutrients, light, oxygen and others. We test the usefulness of this definition on observations of the crustacean zooplankton Daphnia pulicaria. In one set of experiments, D. pulicaria is infested with the pathogen Vibrio cholerae, the causative agent of cholera. We find that infested D. pulicaria under light exposure have a significantly greater ecological temperature, which puts them at a greater risk of detection by visual predators. In a second set of experiments, we observe D. pulicaria in cold and warm water, and in darkness and under light exposure. Overall, our ecological temperature is a good discriminator of the crustacean's swimming behavior.

The high speed impact of a droplet on a bulk fluid at high We is not well understood but is relevant to the production of marine aerosol by raindrop impact on the sea surface. These splashes produce a subsurface cavity and a crown which closes into a bubble canopy, but a floating layer of immiscible oil, such as a crude oil slick, alters splash dynamics. The effects of oil layer fluid properties and thickness and droplet size and impact speed are examined by high speed visualization. Oil layer rupture and crown behavior are classified by dimensional scaling. The subsurface cavity volume for impact on thick layers is shown to depend on Re, though canopy formation at high Re introduces a competing We effect since rapid canopy closure is found to retard cavity expansion. Time-resolved kinematic measurements show that thin crude oil slicks similarly alter crown closure and cavity growth. The size and spatial distributions of airborne droplets are examined using high speed holographic microscopy. Droplets have a bimodal distribution with peaks at 50 and 225 μm and are clustered by size at different elevation angles. Small droplets (50 μm) are ejected primarily at shallow angles, indicating production by splashing within the first 100 μs and by breakup of microligaments. Larger droplets (225 μm) are found at steeper elevation angles, indicating later production by capillary instability acting on large ligaments protruding upward from the crown. Intermittent droplet release while the ligaments grow and sweep upward is thought to contribute to the size-dependent spatial ordering. Greater numbers of small droplets are produced at high elevation angles when a crude oil layer is present, indicating satellite droplet formation from ligament breakup. A crude oil layer also increases the target fluid Oh, leading to creation of an intact ejecta sheet, which then ruptures to form aerosolized oil droplets.

It is often observed that small drops or bubbles detach from the interface separating two co-flowing immiscible fluids. The size of these drops or bubbles can be orders of magnitude smaller than the length scales of the parent fluid mass. Examples are tip-streaming from drops or coaxial jets in microfluidics, selective withdrawal, ‘skirt’ formation around bubbles or drops, and others. It is argued that these phenomena are all reducible to a common instability that can occur due to a local convergence of streamlines in the neighbourhood of a zero-vorticity point or line on the interface. When surfactants are present, this converging flow tends to concentrate them in these regions weakening the effect of surface tension, which is the only mechanism opposing the instability. Several analytical and numerical calculations are presented to substantiate this interpretation of the phenomenon. In addition to some idealized cases, the results of two-dimensional simulations of co-flowing jets and a rising drop are presented.

Bacterial attachment to a fluid interface can lead to the formation of a film with physicochemical properties that evolve with time. We study the time evolution of interface (micro)mechanics for interfaces between oil and bacterial suspensions by following the motion of colloidal probes trapped by capillarity to determine the interface microrheology. Initially, active bacteria at and near the interface drive superdiffusive motion of the colloidal probes. Over timescales of minutes, the bacteria form a viscoelastic film which we discuss as a quasi-two-dimensional, active, glassy system. To study late stage mechanics of the film, we use pendant drop elastometry. The films, grown over tens of hours on oil drops, are expanded and compressed by changing the drop volume. For small strains, by modeling the films as 2D Hookean solids, we estimate the film elastic moduli, finding values similar to those reported in the literature for the bacteria themselves. For large strains, the films are highly hysteretic. Finally, from wrinkles formed on highly compressed drops, we estimate film bending energies. The dramatic restructuring of the interface by such robust films has broad implications, e.g. in the study of active colloids, in understanding the community dynamics of bacteria, and in applied settings including bioremediation.

We determined the contributions of photooxidation and biodegradation to the weathering of Light Louisiana Sweet crude oil by incubating surface water from the Deepwater Horizon site under natural sunlight and temperature conditions. N-alkane biodegradation rate constants were ca. ten-fold higher than the photooxidation rate constants. For the 2–3 ring and 4–5 ring polycyclic aromatic hydrocarbons (PAHs), photooxidation rate constants were 0.08–0.98 day⁻¹ and 0.01–0.07 day⁻¹, respectively. The dispersant Corexit enhanced degradation of n-alkanes but not of PAHs. Compared to biodegradation, photooxidation increased transformation of 4–5 ring PAHs by 70% and 3–4 ring alkylated PAHs by 36%. For the first time we observed that sunlight inhibited biodegradation of pristane and phytane, possibly due to inhibition of the bacteria that can degrade branched-alkanes. This study provides quantitative measures of oil degradation under relevant field conditions crucial for understanding and modeling the fate of spilled oil in the northern Gulf of Mexico.

This study evaluated impacts of the BP Deepwater Horizon (DWH) oil spill on petroleum hydrocarbons in surface waters of the Louisiana continental shelf in northern Gulf of Mexico. Surface water (~top 5 cm) without visible oil was collected from three cruises in May 2010 during the oil spill, August 2010 after the well was capped, and May 2011 one year after the spill. Concentrations of total dissolved n-alkanes (C₉–C₃₅) in surface seawater were more than an order of magnitude higher in May 2010 than August 2010 and May 2011, indicating contamination by the DWH oil spill. This conclusion was further supported by more abundant smaller n-alkanes (C₉–C₁₃), together with pristane and phytane, in May than August 2010 samples. In contrast, even carbon-numbered dissolved n-alkanes (C₁₄–C₂₀) dominated the May 2011 samples, and this distribution pattern of dissolved n-alkanes is the first documentation for water samples in the northern Gulf of Mexico. However, this pattern was not observed in May 2011 suspended particles except for Sta. OSS. This decoupling between dissolved and particle compositions suggests that either these even carbon-numbered n-alkanes originated from bacteria rather than algae, or that the alkanes in the shelf were transported from elsewhere. Concentrations of polycyclic aromatic hydrocarbons (PAHs) in suspended particles were 5 times higher on average in May 2010 (83–252 ng L⁻¹) than May 2011 (7.2–83 ng L⁻¹), also indicating contamination by the DWH oil spill. Application of a biomarker ratio of 17α(H),21β(H)-30-norhopane over 17α(H),21β(H)-hopane confirmed that suspended particles from at least two stations were contaminated by the DWH oil spill in May 2010. Taken together, these results showed that surface waters of the sampling area in May 2010 were contaminated by the oil spill, but also that rapid weathering and/or physical dilution quickly reduced hydrocarbon levels by August 2010.

Better understanding of bacteria environment interactions in the context of biofilm formation requires accurate 3-dimentional measurements of bacteria motility. Digital Holographic Microscopy (DHM) has demonstrated its capability in resolving 3D distribution and mobility of particulates in a dense suspension. Due to their low scattering efficiency, bacteria are substantially difficult to be imaged by DHM. In this paper, we introduce a novel correlation-based de-noising algorithm to remove the background noise and enhance the quality of the hologram. Implemented in conjunction with DHM, we demonstrate that the method allows DHM to resolve 3-D E. coli bacteria locations of a dense suspension (>107 cells/ml) with submicron resolutions (<0.5 µm) over substantial depth and to obtain thousands of 3D cell trajectories.

Understanding how bacteria move close to surfaces is crucial for a broad range of microbial processes including biofilm formation, bacterial dispersion, and pathogenic infections. We used digital holographic microscopy to capture a large number (>103) of three-dimensional Escherichia coli trajectories near and far from a surface. We found that within 20  μm from a surface tumbles are suppressed by 50% and reorientations are largely confined to surface-parallel directions, preventing escape of bacteria from the near-surface region. A hydrodynamic model indicates that the tumble suppression is likely due to a surface-induced reduction in the hydrodynamic force responsible for the flagellar unbundling that causes tumbling. These findings imply that tumbling does not provide an effective means to escape trapping near surfaces.

This study evaluated impacts of the BP Deepwater Horizon (DWH) oil spill on petroleum hydrocarbons in surface waters of the Louisiana continental shelf in northern Gulf of Mexico. Surface water (~top 5 cm) without visible oil was collected from three cruises in May 2010 during the oil spill, August 2010 after the well was capped, and May 2011 one year after the spill. Concentrations of total dissolved n-alkanes (C₉–C₃₅) in surface seawater were more than an order of magnitude higher in May 2010 than August 2010 and May 2011, indicating contamination by the DWH oil spill. This conclusion was further supported by more abundant smaller n-alkanes (C₉–C₁₃), together with pristane and phytane, in May than August 2010 samples. In contrast, even carbon-numbered dissolved n-alkanes (C₁₄–C₂₀) dominated the May 2011 samples, and this distribution pattern of dissolved n-alkanes is the first documentation for water samples in the northern Gulf of Mexico. However, this pattern was not observed in May 2011 suspended particles except for Sta. OSS. This decoupling between dissolved and particle compositions suggests that either these even carbon-numbered n-alkanes originated from bacteria rather than algae, or that the alkanes in the shelf were transported from elsewhere. Concentrations of polycyclic aromatic hydrocarbons (PAHs) in suspended particles were 5 times higher on average in May 2010 (83–252 ng L⁻¹) than May 2011 (7.2–83 ng L⁻¹), also indicating contamination by the DWH oil spill. Application of a biomarker ratio of 17α(H),21β(H)-30-norhopane over 17α(H),21β(H)-hopane confirmed that suspended particles from at least two stations were contaminated by the DWH oil spill in May 2010. Taken together, these results showed that surface waters of the sampling area in May 2010 were contaminated by the oil spill, but also that rapid weathering and/or physical dilution quickly reduced hydrocarbon levels by August 2010.

Our knowledge of the lethal and sublethal effects of dispersants and dispersed crude oil on meroplanktonic larvae is limited despite the importance of planktonic larval stages in the life cycle of benthic invertebrates. We determined the effects of Light Louisiana Sweet crude oil, dispersant Corexit 9500A, and dispersant-treated crude oil on the survival and growth rates of nauplii of the barnacle Amphibalanus improvisus and tornaria larvae of the enteropneust Schizocardium sp. Growth rates of barnacle nauplii and tornaria larvae were significantly reduced after exposure to chemically dispersed crude oil and dispersant Corexit 9500A at concentrations commonly found in the water column after dispersant application in crude oil spills. We also found that barnacle nauplii ingested dispersed crude oil, which may have important consequences for the biotransfer of petroleum hydrocarbons through coastal pelagic food webs after a crude oil spill. Therefore, application of chemical dispersants increases the impact of crude oil spills on meroplanktonic larvae, which may affect recruitment and population dynamics of marine benthic invertebrates.