Field fluorometers for assessing oil dispersion at sea.

Oil dispersion by the application of chemical dispersants is an important tool in oil spill response, but it is difficult to quantify in the field in a timely fashion that is useful for coordinators and decision-makers. One option is the use of rugged portable field fluorometers that can deliver essentially instantaneous results if access is attainable. The United States Coast Guard has suggested, in their Special Monitoring of Applied Response Technologies (SMART) protocols, that successful oil dispersion can be identified by a five-fold increase in oil fluorescence. Here we test three commercial fluorometers with different excitation/emission windows (SeaOWL, Cyclops 7FO, and Cyclops 7F-G) that might prove useful for such applications. Results show that they have significantly different dynamic ranges for detecting oil and that using them (or similar instruments) in combination is probably the best option for successfully assessing the effectiveness of oil dispersion operations. Nevertheless, the rapid dilution of dispersed oil means that measurements must be made within an hour or two of dispersion, suggesting that one feasible scenario would be monitoring ship-applied dispersants by vessels following close behind the dispersant application vessel. Alternatively, autonomous submersibles might be pre-deployed to monitor aerial dispersant application, although the logistical challenges in a real spill would be substantial.

Temporal chemical composition changes in water below a crude oil slick irradiated with natural sunlight.

Photooxidation can alter the environmental fate and effects of spilled oil. To better understand this process, oil slicks were generated on seawater mesocosms and exposed to sunlight for 8 days. The molecular composition of seawater under irradiated and non-irradiated oil slicks was characterized using ion mobility spectrometry-mass spectrometry and polyaromatic hydrocarbons analyses. Biomimetic extraction was performed to quantify neutral and ionized constituents. Results show that seawater underneath irradiated oil showed significantly higher amounts of hydrocarbons with oxygen- and sulfur-containing by-products peaking by day 4-6; however, concentrations of dissolved organic carbon were similar. Biomimetic extraction indicated toxic units in irradiated mesocosms increased, mainly due to ionized components, but remained <1, suggesting limited potential for ecotoxicity. Because the experimental design mimicked important aspects of natural conditions (freshly collected seawater, natural sunlight, and relevant oil thickness and concentrations), this study improves our understanding of the effects of photooxidation during a marine oil spill.

Proof of concept study for in-situ burn application using conventional containment booms - Design of Burning Tongue.

In situ burning (ISB) hasn't been widely used for offshore oil spill response for various reasons. We present a feasibility study for a new ISB method - the Burning Tongue (BT) concept. We conducted scaled experiments in the Ohmsett wave tank to demonstrate its feasibility. We produced a 35-m long "tongue" of burnable oil (average oil thickness 4.2 mm - above the thickness needed for ISB) by towing a conventional boom (with a 12″ (0.3 m) deep skirt) partially filled with crude oil and then released the oil through a 6″ (0.15 m) wide opening at the apex. We found that the boom movement produced a convergence zone just downstream that kept released oil thick and also pulled oil that entrained under the boom skirt into the thick "tongue" of oil. CFD modeling was performed to explain the flow hydrodynamics and the formation of the convergence zone, which indicates the phenomenon is universal. We used small harbor boom only partially filled with oil for this study and believe that a full-scale marine boom filled with oil would achieve an even thicker "burning tongue." The BT concept could make ISB more widely used for oil spill response in offshore areas.

Investigation of the spreading tendency of emulsified oil slicks on open systems.

Properties and stability of water-in-oil emulsions influence oil behavior and response decisions. Closed-system lab protocols that assess emulsion stability cannot fully represent oil behavior in the open sea. We developed a novel test system that allows emulsions to spread over a laboratory flat pan. Nine highly weathered oils were studied and seven formed very stable emulsions in a closed-system. Results from our tests show that these oils underwent significant spreading unless the testing temperature were well below the oils' pour point. These findings indicate that emulsions may be less stable than laboratory tests indicate under some at-sea conditions (e.g. offshore in either high-energy or low-energy seas). Oil thinning due to spreading causes emulsions to break and the resulting thin oil film would be more susceptible to natural dispersion. Additional carefully designed laboratory and controlled field tests are needed to determine the operational relevance of our findings.

Oil Irradiation Experiments Document Changes in Oil Properties, Molecular Composition, and Dispersant Effectiveness Associated with Oil Photo-Oxidation.

While chemical dispersants are a powerful tool for treating spilled oil, their effectiveness can be limited by oil weathering processes such as evaporation and emulsification. It has been suggested that oil photo-oxidation could exacerbate these challenges. To address the role of oil photo-oxidation in dispersant effectiveness, outdoor mesocosm experiments with crude oil on seawater were performed. Changes in bulk oil properties and molecular composition were quantified to characterize oil photo-oxidation over 11 days. To test relative dispersant effectiveness, oil residues were evaluated using the Baffled Flask Test. The results show that oil irradiation led to oxygen incorporation, formation of oxygenated hydrocarbons, and higher oil viscosities. Oil irradiation was associated with decreased dispersant efficacy, with effectiveness falling from 80 to <50% in the Baffled Flask Test after more than 3 days of irradiation. Increasing photo-oxidation-induced viscosity seems to drive the decreasing dispersant effectiveness. Comparing the Baffled Flask Test results with field data from the Deepwater Horizon oil spill showed that laboratory dispersant tests underestimate the dispersion of photo-oxidized oil in the field. Overall, the results suggest that prompt dispersant application (within 2-4 days), as recommended by current oil spill response guidelines, is necessary for effective dispersion of spilled oil.

Oil droplet formation and vertical transport in the upper ocean.

The dispersion of oil droplets near ocean surface is important for evaluating the impact to the environment. Under breaking wave conditions, the surface oil experiences mainly two processes: the generation of oil droplets at/near the water surface, and the transport of oil droplets due to ocean dynamics. We investigated the vertical behavior by incorporating the transport equation and the VDROP model. The transport equation adopted the ocean dynamics by K-profile parameterization (KPP) and the impact of additional turbulence by imposing the energy dissipation rate on the ocean surface. The oil droplet distribution was obtained, and the entrained distribution and entrainment rate was computed. The results shows that although the entrained distribution and the entrainment rate shares certain consistency with previous studies, divergences are also noticed. Accordingly, the model that describes the physics should be adopted to avoid incorrect qualification of the oil concentration dispersed in the ocean.

Deepwater Horizon 2010: Subsea dispersants protected responders from VOC exposure.

Controversy remains on the use of Sub-Sea Dispersant Injection (SSDI) during the Deepwater Horizon (DWH) spill to minimize the exposure of responders on surface vessels to volatile organic compounds (VOC). Here, we use extensive evidence (>90,000 VOC measurements) collected near the oil well MC252 site during the DWH spill and demonstrate at a high level of statistical confidence that SSDI enhanced the safety and health conditions of the responders at the water surface through the reduction of airborne VOC concentrations in a dose-dependent manner. VOC levels on ships' decks were clearly diminished (p < 0.001) during subsea dispersant use, and incidents of peak concentrations (>50 ppm VOC) that could have been an immediate concern to worker health were reduced by a factor of ~6 to 19 when dispersants were delivered at the intended rate. SSDI thus played an important role in minimizing potential exposure to VOC, and should be embedded in guidelines and regulations for dispersant use.

Effectiveness of mechanical recovery for large offshore oil spills.

Mechanical recovery for large offshore oil spills (defined as the marine environment over 10 km from shore outside of bays, lagoons, and marinas) depends on oil behavior, environmental conditions, equipment specifications, and operational issues. These factors limit oil recovery with booms and skimmers. The "rule of thumb" has been that 10-30% of the total oil spilled can be recovered. This paper describes a review of historical oil spills that found only between 2 and 6% of the total oil spilled was recovered. The limiting factors affecting mechanical recovery in offshore settings include environmental conditions, oil behavior, and logistics. Mechanical recovery will always be an important tool for spill response, especially in nearshore and in-port settings, as well as locations with sensitivity to chemical dispersants and/or in situ burning. However, its application in large offshore spills will generally result in recovery of only a fraction of the spilled oil.

On the transport and modeling of dispersed oil under ice.

Theoretical arguments and numerical investigations were conducted to understand the transport of oil droplets under ice. It was found that the boundary layer (BL) in the water under ice produces a downward velocity that reaches up to 0.2% of horizontal current speed, and is, in general, larger than the rise velocity of 70 µm oil droplets. The eddy diffusivity was found to increase with depth and to decrease gradually afterward. Neglecting the gradient of eddy diffusivity when conducting Lagrangian transport of oil droplets would result in an unphysical spatial distribution. When the downward velocity of water was neglected, oil accumulated at the water-ice interface regardless of the attachment efficiency. The lift force was found to scrape off droplets of the ice, especially for droplets ≤ 70 µm. These findings suggest that previous oil spill simulations may have overestimated the number of small droplets (≤70 µm) at the water-ice interface.

Comparative Risk Assessment of spill response options for a deepwater oil well blowout: Part 1. Oil spill modeling.

Oil spill model simulations of a deepwater blowout in the Gulf of Mexico De Soto Canyon, assuming no intervention and various response options (i.e., subsea dispersant injection SSDI, in addition to mechanical recovery, in-situ burning, and surface dispersant application) were compared. Predicted oil fate, amount and area of surfaced oil, and exposure concentrations in the water column above potential effects thresholds were used as inputs to a Comparative Risk Assessment to identify response strategies that minimize long-term impacts. SSDI reduced human and wildlife exposure to volatile organic compounds; dispersed oil into a large water volume at depth; enhanced biodegradation; and reduced surface water, nearshore and shoreline exposure to floating oil and entrained/dissolved oil in the upper water column. Tradeoffs included increased oil exposures at depth. However, since organisms are less abundant below 200 m, results indicate that overall exposure of valued ecosystem components was minimized by use of SSDI.

Evaluation of the ability of calcite, bentonite and barite to enhance oil dispersion under arctic conditions.

A test program was conducted at laboratory and pilot scale to assess the ability of clays used in drilling mud (calcite, bentonite and barite) to create oil-mineral aggregates and disperse crude oil under arctic conditions. Laboratory tests were performed in order to determine the most efficient conditions (type of clay, MOR (Mineral/Oil Ratio), mixing energy) for OMA (Oil Mineral Aggregate) formation. The dispersion rates of four crude oils were assessed at two salinities. Dispersion was characterized in terms of oil concentration in the water column and median OMA size. Calcite appeared to be the best candidate at a MOR of 2:5. High mixing energy was required to initiate OMA formation and low energy was then necessary to prevent the OMAs from resurfacing. Oil dispersion using Corexit 9500 was compared with oil dispersion using mineral fines.

Characterization of surface oil thickness distribution patterns observed during the Deepwater Horizon (MC-252) oil spill with aerial and satellite remote sensing.

Knowledge of the spatial distribution of oil thickness patterns within an on-water spill is of obvious importance for immediate spill response activities as well as for subsequent evaluation of the spill impacts. For long-lasting continuous spills like the 2010 3-month Deepwater Horizon (DWH) event in the Gulf of Mexico, it is also important to identify changes in the dominant oil features through time. This study utilized very high resolution (≤5m) aerial and satellite imagery acquired during the DWH spill to evaluate the shape, size and thickness of surface oil features that dominated the DWH slick. Results indicate that outside of the immediate spill source region, oil distributions did not encompass a broad, varied range of thicknesses. Instead, the oil separated into four primary, distinct characterizations: 1) invisible surface films detectable only with Synthetic Aperture Radar imaging because of the decreased surface backscatter, 2) thicker sheen & rainbow areas (<0.005mm), 3) large regional areas of relatively thin, "metallic appearance" films (0.005-0.08mm), and 4) strands of thick, emulsified oil (>1mm) that were consistently hundreds of meters long but most commonly only 10-50m wide. Where present within the slick footprint, each of the three distinct visible oil thickness classes maintained its shape characteristics both spatially (at different distances from the source and in different portions of the slick), and temporally (from mid-May through July 2010). The region over the source site tended to contain a more continuous range of oil thicknesses, however, our results indicate that the continuous injection of subsurface dispersants starting in late May significantly altered (lowered) that range. In addition to characterizing the oil thickness distribution patterns through the timeline of one of the world's largest oil spills, this paper also details the extension of using high resolution aerial imagery to calibrate medium resolution satellite data sources such as USA's Thematic Mapper (30m) to provide larger-scale spatial views of major spills, and discusses implications for utilizing such data for oil spill characterizations and spill response.

Intercomparison of oil spill prediction models for accidental blowout scenarios with and without subsea chemical dispersant injection.

We compare oil spill model predictions for a prototype subsea blowout with and without subsea injection of chemical dispersants in deep and shallow water, for high and low gas-oil ratio, and in weak to strong crossflows. Model results are compared for initial oil droplet size distribution, the nearfield plume, and the farfield Lagrangian particle tracking stage of hydrocarbon transport. For the conditions tested (a blowout with oil flow rate of 20,000 bbl/d, about 1/3 of the Deepwater Horizon), the models predict the volume median droplet diameter at the source to range from 0.3 to 6mm without dispersant and 0.01 to 0.8 mm with dispersant. This reduced droplet size owing to reduced interfacial tension results in a one to two order of magnitude increase in the downstream displacement of the initial oil surfacing zone and may lead to a significant fraction of the spilled oil not reaching the sea surface.

Use of passive samplers for improving oil toxicity and spill effects assessment.

Methods that quantify dissolved hydrocarbons are needed to link oil exposures to toxicity. Solid phase microextraction (SPME) fibers can serve this purpose. If fibers are equilibrated with oiled water, dissolved hydrocarbons partition to and are concentrated on the fiber. The absorbed concentration (Cpolymer) can be quantified by thermal desorption using GC/FID. Further, given that the site of toxic action is hypothesized as biota lipid and partitioning of hydrocarbons to lipid and fibers is well correlated, Cpolymer is hypothesized to be a surrogate for toxicity prediction. To test this method, toxicity data for physically and chemically dispersed oils were generated for shrimp, Americamysis bahia, and compared to test exposures characterized by Cpolymer. Results indicated that Cpolymer reliably predicted toxicity across oils and dispersions. To illustrate field application, SPME results are reported for oil spills at the Ohmsett facility. SPME fibers provide a practical tool to improve characterization of oil exposures and predict effects in future lab and field studies.

Lab tests on the biodegradation of chemically dispersed oil should consider the rapid dilution that occurs at sea.

Most crude oils spread on open water to an average thickness as low as 0.1 mm. The application of dispersants enhances the transport of oil as small droplets into the water column, and when combined with the turbulence of 1 m waves will quickly entrain oil into the top 1 m of the water column, where it rapidly dilutes to concentrations less than 100 ppm. In less than 24 h, the dispersed oil is expected to mix into the top 10 m of the water column and be diluted to concentrations well below 10 ppm, with dilution continuing as time proceeds. Over the multiple weeks that biodegradation takes place, dispersed oil concentrations are expected to be below 1 ppm. Measurements from spills and wave basin studies support these calculations. Published laboratory studies focused on the quantification of contaminant biodegradation rates have used concentrations orders of magnitude greater than this, as it was necessary to ensure the concentrations of hydrocarbons and other chemicals were higher than the detection limits of chemical analysis. However, current analytical methods can quantify individual alkanes and PAHs (and their alkyl homologues) at ppb and ppm levels. To simulate marine biodegradation of dispersed oil at dilute concentrations commonly encountered in the field, laboratory studies should be conducted at similarly low hydrocarbon concentrations.

The primary biodegradation of dispersed crude oil in the sea.

Dispersants are important tools for stimulating the biodegradation of large oil spills. They are essentially a bioremediation tool - aiming to stimulate the natural process of aerobic oil biodegradation by dispersing oil into micron-sized droplets that become so dilute in the water column that the natural levels of biologically available nitrogen, phosphorus and oxygen are sufficient for microbial growth. Many studies demonstrate the efficacy of dispersants in getting oil off the water surface. Here we show that biodegradation of dispersed oil is prompt and extensive when oil is present at the ppm levels expected from a successful application of dispersants - more than 80% of the hydrocarbons of lightly weathered Alaska North Slope crude oil were degraded in 60 d at 8 °C in unamended New Jersey (USA) seawater when the oil was present at 2.5 ppm by volume. The apparent halftime of the biodegradation of the hydrocarbons was 13.8 d in the absence of dispersant, and 11 d in the presence of Corexit 9500 - similar to rates extrapolated from the field in the Deepwater Horizon response.