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The combustion efficiency of simulated at-sea surface oil burns (in situ burns) was determined in a 63 m3 tank while testing varied boom configurations and air-assist nozzles in the presence and absence of waves. Combustion efficiencies of Alaska North Slope oil based on unburned carbon in the plume emissions ranged from 85% to 93% while values based on oil mass loss ranged from 89% to 99%. A four-fold variation in PM2.5 emission factors was observed from the test conditions. The most effective burns in terms of reduced emissions and post-burn residue concentration of total petroleum hydrocarbons were those that had high length to width boom ratios resulting in higher flame front surface area exposure to ambient air. The amount of oil mass lost was not related to any combustion efficiency parameters measured in the plume, representing a potential tradeoff between unburnt oil and air pollution.

Chemical dispersant formulations typically provide maximum oil dispersion in waters between 30–40 ppt (parts per thousand) salt content, which encompasses typical ocean salinity (~34 ppt). As a result, most laboratory studies of oil dispersion effectiveness (DE) are conducted at low to average ocean salinity. Ocean salinity can vary locally from below 20 ppt during ice and snow melt, to extremely high (over 100 ppt) during freeze up periods or within natural brine pools in deeper waters. In this study, the influence of salinity on DE was evaluated using the baffled flask test (BFT) at a dispersant-to-oil ratio (DOR) of 1:25. Benchtop experiments were conducted with Alaskan North Slope (ANS) crude oil in the presence or absence of chemical dispersant at 5 and 25°C and varying salinities (0.2 to 125 ppt). In addition to DE as determined by BFT, oil droplet size distribution (DSD) and fluorescence intensity was measured via a LISST-100X particle size analyzer (Sequoia Scientific, Inc., Bellevue, WA) and ECO fluorometer (Sea Bird - WET Labs, Inc.; Philomath, OR), respectively. Results indicate that in the presence of dispersant, maximum DE occurred at 25ppt, and decreases above and below this salinity. Concentration of small droplets (

Historically, visual observation is an emergency responder's first ‘tool’ in identifying spilled oil. Optical detection has since expanded to include a myriad of signals from space, aircraft, drone, vessel and submersible platforms that can provide critical information for decision-making during spill response efforts. Spill monitoring efforts below the air-water interface have been vastly improved by advances with in situ optical sensors and vehicle platform technology. Optical techniques using fluorescence, scattering, and holography offer a means to determine dissolved versus droplet fractions, provide oil concentration estimates and serve as proxies for dispersion efficiency. For subsurface spills over large space and time scales, Autonomous Underwater Vehicles (AUVs) can be used to provide subsurface plume footprints and estimate oil concentrations. For smaller, more frequent spills, tethered compact Remotely Operated Vehicles (ROVs) may be more appropriate as they are easy to deploy for rapid detection. Two underwater oil detection technologies have been developed: (1) A Remote Environmental Monitoring UnitS (REMUS-600) AUV equipped with fluorescence and backscatter SeaOWL UV-A (Oil-in-Water Locator; Sea-Bird Scientific WET Labs Inc.), holographic imager (HoloCam; SeaScan, Inc), hydrographic information, video camera, CTD and a water/oil sampler. (2) A tethered ROV system (DTG2, Deep Trekker Inc.) equipped with video camera, UviLux (Chelsea Technologies Group, Inc) fluorometer, a CTD and water/oil sampler. Calibration and validation tests of the sensor suite were conducted at the Coastal Response Research Center flume tank (NH, USA). Oil concentration estimates were verified by chemical analysis of hydrocarbons and particle size analysis (LISST 200X, Sequoia, Inc). Operational performance of the ROV platform and sensors was evaluated at the Ohmsett wave tank (NJ, USA). Field performance of the REMUS and sensor suite was evaluated at natural seeps near Santa Barbara, CA. This research demonstrates the forensic value of in situ optical data for improved understanding of the behavior and transport of spilled oil below the air-sea interface.

This paper describes the evolution of the Interagency Coordinating Committee on Oil Pollution Research (ICCOPR) Oil Pollution Research and Technology Plan (R&T Plan) to address changing oil pollution risks associated with advancements in the energy industry practices. The Oil Pollution Act of 1990 (OPA 90) Title VII required development of an R&T Plan to identify the resources needed for the government research programs. The 1992 R&T Plan and its 1997 revision marked a major advancement in how the United States (U.S.) planned its oil pollution research. The first two plans met the needs of their time but were outdated when the Deepwater Horizon oil spill in 2010 revealed a wide range of new research needed to address the risks associated with advancements in industry practices. ICCOPR responded to the new challenges by revising the Charter and establishing a six-year R&T Plan revision cycle. In September 2015, ICCOPR released the FY 2015–2021 R&T Plan, which established a new baseline plan for current and future planning. This paper describes the structured review process used to analyze more than 900 research needs identified since OPA 90 was enacted. The paper explains the new research classification process that established four Classes, 25 Standing Research Areas (SRAs), and 150 priority research needs in the R&T Plan. ICCOPR is working on the first revision in the new six-year planning cycle to cover the FY2022–2027 timeframe. The paper describes the factors being evaluated to update the list of priority needs. These factors include how well current priorities have been addressed and new or emerging oil pollution risks. An update on the status of addressing the priorities will be presented, including the number of SRAs addressed by ICCOPR agencies and others.

The baffled flask test (BFT) has been proposed by United States Environmental Protection Agency to be adopted as the official standard protocol for testing dispersant effectiveness. The mixing energy in the baffled flask is investigated in this paper. Particle image velocimetry (PIV) was used to measure the water velocity in the flask placed at an orbital shaker that was rotated at seven rotation speeds: 100, 125, 150, 160, 170, 200, and 250 rpm. Two dimensional velocity fields in large and small vertical cross sections of the flask for each rotation speed were obtained. The one-dimensional (1D) energy spectra indicates the existence of inertial subrange. The estimated average energy dissipation rates were in the range 7.65×10(−3) to 4 W/kg for rotation speeds of Ω=100–250 rpm, of which it is larger than the one estimated by prior studies using single-point velocity measurement techniques for Ω=100 and 200 rpm. Factors such as instruments used, velocity components measured, and different analysis methods could contribute to the discrepancies in the results. The Kolmogorov scale estimated in this study for all seven rotation speeds approached the size of oil droplets observed at sea, which is 50–400 μm. The average energy dissipation rate, ε and Kolmogorov microscale, η, in the flasks were correlated to the rotation speed, and it was found that [Formula: see text] Exp (0.043Ω) with R(2) = 0.97 and [Formula: see text] Exp (−0.015Ω) with R(2) = 0.98.

Cyanobacterial harmful algal blooms (cyanoHAB) cause human and ecological health problems in lakes worldwide. The timely distribution of satellite-derived cyanoHAB data is necessary for adaptive water quality management and for targeted deployment of water quality monitoring resources. Software platforms that permit timely, useful, and cost-effective delivery of information from satellites are required to help managers respond to cyanoHABs. The Cyanobacteria Assessment Network (CyAN) mobile device application (app) uses data from the European Space Agency Copernicus Sentinel-3 satellite Ocean and Land Colour Instrument (OLCI) in near real-time to make initial water quality assessments and quickly alert managers to potential problems and emerging threats related to cyanobacteria. App functionality and satellite data were validated with 25 state health advisories issued in 2017. The CyAN app provides water quality managers with a user-friendly platform that reduces the complexities associated with accessing satellite data to allow fast, efficient, initial assessments across lakes.

Chemical dispersants are one of many tools used to mitigate the overall environmental impact of oil spills. In principle, dispersants break up floating oil into small droplets that disperse into the water column where they are subject to multiple fate and transport processes. The effectiveness of dispersants typically decreases as oil weathers in the environment. This decrease in effectiveness is often attributed to evaporation and emulsification, with the contribution of photochemical weathering assumed to be negligible. Here, we aim to test this assumption using Macondo well oil released during the Deepwater Horizon spill as a case study. Our results indicate that the effects of photochemical weathering on Deepwater Horizon oil properties and dispersant effectiveness can greatly outweigh the effects of evaporative weathering. The decrease in dispersant effectiveness after light exposure was principally driven by the decreased solubility of photo-oxidized crude oil residues in the solvent system that com...

Although great progress has been made to advance the scientific understanding of oil spills, tools for integrated assessment modeling of the long-term impacts on ecosystems, socioeconomics and human health are lacking. The objective of this study was to develop a conceptual framework that could be used to answer stakeholder questions about oil spill impacts and to identify knowledge gaps and future integration priorities. The framework was initially separated into four knowledge domains (ocean environment, biological ecosystems, socioeconomics, and human health) whose interactions were explored by gathering stakeholder questions through public engagement, assimilating expert input about existing models, and consolidating information through a system dynamics approach. This synthesis resulted in a causal loop diagram from which the interconnectivity of the system could be visualized. Results of this analysis indicate that the system naturally separates into two tiers, ocean environment and biological ecosystems versus socioeconomics and human health. As a result, ocean environment and ecosystem models could be used to provide input to explore human health and socioeconomic variables in hypothetical scenarios. At decadal-plus time scales, the analysis emphasized that human domains influence the natural domains through changes in oil-spill related laws and regulations. Although data gaps were identified in all four model domains, the socioeconomics and human health domains are the least established. Considerable future work is needed to address research gaps and to create fully coupled quantitative integrative assessment models that can be used in strategic decision-making that will optimize recoveries from future large oil spills.

Water quality measures for inland and coastal waters are available as discrete samples from professional and volunteer water quality monitoring programs and higher-frequency, near-continuous data from automated in situ sensors. Water quality parameters also are estimated from model outputs and remote sensing. The integration of these data, via data assimilation, can result in a more holistic characterization of these highly dynamic ecosystems, and consequently improve water resource management. It is becoming common to see combinations of these data applied to answer relevant scientific questions. Yet, methods for scaling water quality data across regions and beyond, to provide actionable knowledge for stakeholders, have emerged only recently, particularly with the availability of satellite data now providing global coverage at high spatial resolution. In this paper, data sources and existing data integration frameworks are reviewed to give an overview of the present status and identify the gaps in existing frameworks. We propose an integration framework to provide information to user communities through the the Group on Earth Observations (GEO) AquaWatch Initiative. This aims to develop and build the global capacity and utility of water quality data, products, and information to support equitable and inclusive access for water resource management, policy and decision making.

In this paper, we present the analysis of an underwater horizontal oil jet experimental measurement and Computational Fluid Dynamics (CFD) using the Reynolds Averaged Navier Stokes (RANS) equations. Two oil subsurface releases were conducted: one with crude oil and another with crude oil premixed with dispersant at the dispersant to oil ratio (DOR) of 1:20. The jet profile was captured by a camera at moderate resolution, and the instantaneous velocity was measured by a Vectrino Profiler. The velocity components, turbulence kinetic energy, and turbulence dissipation rate from the experiment agreed well with those from the CFD simulation using the k-epsilon turbulence model. The spread angle of the jet was found to be around 21° and 24° from the experiment measurement, for oil without dispersant and oil with dispersant, respectively. The latter is close to the angle of miscible jets at 23°. The jet profile of oil with dispersant had a smaller buoyancy than that without dispersant, which is probably due to the large water entrainment for the oil with dispersant jet. The cross sections of the jet for both cases gradually became flattened with distance, as the plume turned upward.

Modeling the movement of oil released underwater is a challenging task due to limitations in measuring the hydrodynamics in an oil-water system. In this work, we conducted an experiment of horizontal release of oil without and with dispersant. The model VDROP-J was used and compared to the model JETLAG, a miscible plume trajectory model. Both models were found to reproduce the oil jet hydrodynamics for oil without and with dispersant. The predicted DSD from VDROP-J matched closely observation for untreated oil. For oil with dispersant, experimental results have shown evidence that tip streaming occurred. For this purpose, a new conceptual module was developed in VDROP-J to capture the tip streaming phenomenon and an excellent match was achieved with observation. This study is the first to report tip streaming occurring in underwater oil jets, which should have consequences on predicting the DSD when dispersant are used on an underwater oil release. © 2017 American Institute of Chemical Engineers AIChE J, 2017

Optical measurements have been used during oil spill response for more than three decades to determine oil presence in slicks and plumes. Oil surveillance approaches range from simple (human eyeball) to the sophisticated (sensors on AUVs, aircraft, satellites). In situ fluorometers and particle size analyzers were deployed during the Deepwater Horizon (DWH) Gulf of Mexico oil spill to track shallow and deep subsea plumes. Uncertainties regarding instrument specifications and capabilities during DWH necessitated performance testing of sensors exposed to simulated, dispersed oil plumes. Seventy-two wave tank experiments were conducted at the Bedford Institute of Oceanography. Simulated were oil releases with varying parameters such as oil release rate, oil temperature (reservoir temp ~ 80 °C), water temperature (15 °C), oil type, dispersant type (Corexit 9500 and Finasol OSR52) and dispersant to oil ratio (DOR). Plumes of Alaskan North Slope Crude (ANS), South Louisiana Crude (SLC) and IFO-120 oils were tracked using in situ fluorescence, droplet size distribution (DSD), total petroleum hydrocarbons (TPH) and benzene-toluene-ethylbenzene-xylene (BTEX). For the lighter SLC, bimodal droplet size with mean diameter < 70 μm was achieved for 1:20 and 1:100 DOR, regardless of water temperature. Similarly, the medium ANS crude exhibited mean droplet diameter

Chemical dispersant agents reduce the interfacial tension between oil and water, and increase the surface area to volume ratio of oil droplets thus facilitating the biodegradation of spilled oil. Dispersants are composed of surface active molecules known as surfactants and various commercial products contain Dioctyl Sulfosuccinate (DOSS) as the active surfactant ingredient. Since previous laboratory studies were conducted at oil and dispersant concentrations significantly higher (~0.7 g/L oil with Dispersant to Oil Ratio (DOR) of 1:25) than those typically found in field conditions, experiments were conducted at low levels of oil and dispersant (28 μg/L oil with DOR of 1:25) in order to determine the degradation trends at environmentally relevant concentrations. Experiments were conducted using two crude oils (Alaskan North Slope (ANS) and Endicott) and two dispersant products (Corexit 9500 and Finasol OSR 52) to study the biodegradation of dispersants and dispersed oil and oil alone samples were used as controls. Two oil degrading cultures, isolated from the surface (meso) and deep sea (cryo) of the Gulf of Mexico, were enriched on crude oil at 25 and 5 °C and were used as the inocula. The biodegradation experiments were performed at 5 °C for 56 days and at 25 °C for 48 days using sterile GP2 artificial seawater as the media. The time series concentration of DOSS, the primary surfactant in the dispersants was monitored using LC-MS/MS in addition to the oil concentration which was measured using GC-MS/MS. Although the initial concentration of DOSS in Finasol OSR 52 was 20% higher than in Corexit 9500, over 95% of the anionic surfactant fraction was metabolized for both types of dispersant products by the end of the experiment at 25 °C while it persisted at 5 °C. The effect of dispersant and oil type on microbial community structure was also analyzed using PCR analysis. Results indicated that the abundance of Thalassospira correlated well with hydrocarbon degradation trends. The results from this study significantly expands on our understanding of biodegradation of DOSS, dispersed, and non-dispersed oil and also provides information regarding bacterial community composition.

2017-271 In recent years, diluted bitumen (or dilbit) has become an important source of hydrocarbon-based fuel. While information on the degradation of crude oils has been well researched, dilbit degradation has been studied at a much lesser extent. The objective of this study was to compare biodegradation of dilbit with a conventional crude oil (CCO) under various conditions. Two different microcosm experiments were set up, one containing a mixed culture acclimated to dilbit (Kalamazoo River Enrichment, KRC) and the other having a mixed culture enriched on soil contaminated with hydrocarbons (Anderson Ferry Enrichment, AFC). The microcosms were run for 60 d at 25 °C and for 72 days at 5 °C in flasks containing sterile Bushnell Hass broth and naturally dispersed oil. Each flask was inoculated with the KRC and AFC mixed cultures, and rotated on an orbital shaker (200 rpm) at the above stated temperatures. On each sampling day, triplicates were sacrificed to determine the residual hydrocarbon concentration. Additionally, some samples were used to determine the bacterial composition using 16S rRNA gene sequencing analysis. Hydrocarbon analysis (alkanes and PAHs) was performed by gas chromatography/mass spectrometry (GC/MS/MS). Higher degradation rates were achieved at 25 °C as compared to 5 °C. All the enrichments metabolized CCO as well dilbit, but the nature and extent of the degradation was distinct. KRC meso culture was the most effective among all, as it completely removed alkanes and most of the PAHs. AFC enrichment performed differently at the two temperatures; an acclimation period (8 d) was observed at 5 °C while there was no lag at 25 °C. KRC cryo culture as well as AFC culture at both temperatures degraded alkanes completely while they were not able to metabolize heavier fractions of the oil (C2–4 homologues of 3- and 4-ring compounds). All cultures showed the presence of diverse oil degrading bacteria and the differences in their compositions affected the biodegradation. Although dilbit was biodegraded, for all the treatments except AFC at 5 °C, the rate of degradation and the extent of degradation was greater for CCO owing to the higher concentrations of lighter hydrocarbons.

A new laboratory testing protocol for evaluating effectiveness of solidifiers in removing crude oil slicks on the water surface has been developed by the U.S. Environmental Protection Agency (EPA). Since an assessment of a testing protocol requires validation through an inter laboratory study with several independent research partners, a round-robin test was performed by five operators across two laboratories. The protocol was qualitatively and quantitatively evaluated to determine if it can satisfactorily differentiate product effectiveness, while still accounting for experimental and operational errors. Each operator evaluated the efficiency of six solidifier products with Arabian Light, Endicott and IFO 120 crude oils. All the experiments were carried out in triplicates and, additionally, an oil alone control sample was run for quality control purposes. The five operators were provided with all the supplies required to conduct the experiment and a detailed standard operating procedure. The results were collected and analyzed statistically to quantify repeatability and reproducibility. The average repeatability and reproducibility standard deviations were 5.1, 2.7, and 3.3% and 11.2, 10.1, and 13.1% for Arabian Light, Endicott and IFO, respectively. The within-operator error was ≤ 5% regardless of operator and oil type. Due to the difficulty and uncertainty associated with the separation of the solidified and un-solidified mass, the between-operator error was around 10%. The oil alone control had an average repeatability and reproducibility standard deviation of 4.8 and 6.1%, respectively. The variability among operators was also examined with h-statistics and the differences in operator means were found to be statistically insignificant. The variability is deemed acceptable for purposes of differentiating effective from ineffective solidifier products in the laboratory. The results from this round robin experiment will serve as an initial screening tool for the solidifier products in the market and will also help response teams determine the desirability and appropriateness of using a specific solidifier for oil spill remediation.

Water Quality (WQ) condition is based on ecosystem stressor indicators (e.g. water clarity) which are biogeochemically important and critical when considering the Deepwater Horizon oil spill restoration efforts under the 2012 RESTORE Act. Nearly all of the proposed RESTORE projects list restoring WC as a goal, but 90% neglect water clarity. Here, dynamics of optical constituents impacting clarity are presented from a 2009–2011 study within Pensacola, Choctawhatchee, St. Andrew and St. Joseph estuaries (targeted RESTORE sites) in Northwest Florida. Phytoplankton were the smallest contribution to total absorption (a(t-w)PAR) at 412 nm (5–11%), whereas colored dissolved organic matter was the largest (61–79%). Estuarine a(t-w)PAR was significantly related to light attenuation (K(d)PAR), where individual contributors to clarity and the influence of climatic events were discerned. Provided are conversion equations demonstrating interoperability of clarity indicators between traditional State-measured WQ measures (e.g. secchi disc), optical constituents, and even satellite remote sensing for obtaining baseline assessments.

The effects of mixing time and energy on Alaska Northern Slope (ANS) and diluted bitumen Cold Lake Blend (CLB) were investigated using EPA baffled flask test. Dispersion effectiveness and droplet size distribution were measured after 5–120 min. A modeling method to predict the mean droplet size was introduced for the first time to tentatively elucidate the droplet size breakup mechanism. The ANS dispersion effectiveness greatly increased with dispersant and mixing energy. However, little CLB dispersion was noted at small energy input (e = 0.02 Watt/kg). With dispersant, the ANS droplet size distribution reached quasi-equilibrium within 10 min, but that of CLB seems to reach quasi-equilibrium after 120 min. Dispersants are assumed ineffective on high viscosity oils because dispersants do not penetrate them. We provide an alternative explanation based on the elongation time of the droplets and its residence in high intensity zones. When mixing energy is small, CLB did not disperse after 120 min, long enough to allow the surfactant penetration. Our findings suggest that dispersants may disperse high viscosity oils at a rougher sea state and a longer time. The latter could determine how far offshore one can intervene for effective responses to a high viscosity oil spill offshore.

To address knowledge gaps and the lack of benchmarks on the toxicity of dilbit oiled sediments, weathered Cold Lake Blend (CLB) and Western Canadian Select (WCS) were assessed in 10-day sediment tests with the amphipods Hyalella azteca and Leptocheirus plumulosus. Lowest observed effect concentrations (LOECs) and 20% effect levels (EC20s) were determined for wet weight sediment concentrations of TPH and total PAHs normalized to 1% organic carbon. LOECs and EC20s for TPH ranged from 216 to 1165 mg/kg sediment in H. azteca, and from 64 to 75 mg/kg sediment in L. plumulosus. Dilbit LOECs and EC20s for total PAHs ranged from 2.9 to 11.8 mg/kg sediment in H. azteca, and from 0.75 to 0.87 mg/kg in L. plumulosus. Comparison of toxicity-based benchmarks derived from the current study to sediment concentrations from past spills indicate that dilbit spills in aquatic habitats may pose substantial risks to freshwater and estuarine benthic organisms.

Author Posting. © The Oceanography Society, 2016. This article is posted here by permission of The Oceanography Society for personal use, not for redistribution. The definitive version was published in Oceanography 29, no. 3 (2016): 76–87, doi:10.5670/oceanog.2016.72.

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.

Chemical countermeasures for oil spill remediation have to be evaluated and approved by the U.S. Environmental Protection Agency before they may be used to remove or control oil discharges. Solidifiers are chemical agents that change oil from a liquid to a solid by immobilizing the oil and bonding the liquid into a solid carpet-like mass with minimal volume increase. Currently, they are listed as Miscellaneous Oil Spill Control Agent in the National Contingency Plan and there is no protocol for evaluating their effectiveness. An investigation was conducted to test the oil removal efficiency of solidifiers using three newly developed testing protocols. The protocols were qualitatively and quantitatively evaluated to determine if they can satisfactorily differentiate effective and mediocre products while still accounting for experimental error. The repeatability of the three protocols was 15.9, 5.1, and 2.7 %. The protocol with the best performance involved measuring the amount of free oil remaining in the water after the solidified product was removed using an ultraviolet–visible spectrophotometer and it was adopted to study the effect of solidifier-to-oil mass ratio, mixing energy, salinity, and beaker size (i.e., area affected by the spill) on solidifier efficiency. Analysis of Variances were performed on the data collected and results indicated that the beaker size increased spreading, which reduced removal efficiency. Mixing speed appears to impart a ceiling effect with no additional benefit provided by the highest level over the middle level. Salinity was found to be mostly an insignificant factor on performance.

This article reports biodegradation rates for a commercial dispersant, JD-2000, South Louisiana crude oil (SLC) alone, and SLC dispersed with JD-2000 at 5 and 25 °C. Results from the biodegradation experiments revealed that Component X, a chemical marker for JD-2000, rapidly degraded at both temperatures. The application of JD-2000 decreased by half the overall biodegradation rate of aliphatic compounds at 25 °C. At 5 °C, a residual fraction consisting of iso- and n-alkanes (C29-C35) persisted after 56 d. The combination of dispersant and higher temperature resulted in faster removal rates for 2- and 3-ring polycyclic aromatic hydrocarbons. When compared with Corexit 9500, our results suggest that the chemistry of the surfactant (or surfactants) in JD-2000 might have favored oil dissolution (substrate transport to the aqueous phase) as an uptake mechanism over adhesion, which requires direct contact of the biomass with the oil.

The majority of aquatic toxicity data for petroleum products has been limited to a few intensively studied crude oils and Corexit chemical dispersants, and acute toxicity testing in two standard estuarine test species: mysids (Americamysis bahia) and inland silversides (Menidia beryllina). This study compared the toxicity of two chemical dispersants commonly stock piled for spill response (Corexit EC9500A®, Finasol®OSR 52), three less studied agents (Accell Clean®DWD dispersant; CytoSol® surface washing agent; Gelco200® solidifier), and three crude oils differing in hydrocarbon composition (Dorado, Endicott, Alaska North Slope). Consistent with listings on the U.S. National Contingency Plan Product Schedule, general rank order toxicity was greatest for dispersants and lowest for the solidifier. The results indicate that freshwater species can have similar sensitivity as the conventionally tested mysids and silversides, and that the sea urchin (Arbacia punctulata) appears to be a reasonable addition to increase taxa diversity in standardized oil agent testing.

Treatability experiments were conducted to determine the biodegradation of diluted bitumen (dilbit) at 5 and 25 °C for 72 and 60 days, respectively. Microbial consortia obtained from the Kalamazoo River Enbridge Energy spill site were enriched on dilbit at both 5 (cryo) and 25 (meso) oC. On every sampling day, triplicates were sacrificed and residual hydrocarbon concentrations (alkanes and polycyclic aromatic hydrocarbons) were determined by GC MS/MS. The composition and relative abundance of different bacterial groups were identified by 16S rRNA gene sequencing analysis. While some physicochemical differences were observed between the two dilbits, their biodegradation profiles were similar. The rates and extent of degradation were greater at 25 °C. Both consortia metabolized 99.9% of alkanes; however, the meso consortium was more effective at removing aromatics than the cryo consortium (97.5 vs 70%). Known hydrocarbon-degrading bacteria were present in both consortia (Pseudomonas, Rhodococcus, Hydrogenophaga, Parvibaculum, Arthrobacter, Acidovorax), although their relative abundances depended on the temperatures at which they were enriched. Regardless of the dilbit type, the microbial community structure significantly changed as a response to the diminishing hydrocarbon load. Our results demonstrate that dilbit can be effectively degraded by autochthonous microbial consortia from sites with recent exposure to dilbit contamination.

Coloured dissolved organic matter CDOM is relevant for water quality management and may become an important measure to complement future water quality assessment programmes. An approach to derive CDOM using the Moderate Resolution Imaging Spectroradiometer MODIS was developed that may be more accessible to water quality managers by selecting an off-the-shelf software and algorithm with standard atmospheric correction. This study focused on demonstrating the transferability of a remote-sensing reflectance Rrs band ratio algorithm, Rrs667/Rrs488, previously developed to derive CDOM absorption agλ at multiple MODIS wavebands in open ocean and coastal waters to the United States northern Gulf of Mexico estuaries. In situ calibration regressions at 412, 443, 469, and 488 nm had coefficients of determination R2 of 0.76, 0.71, 0.69, and 0.57, respectively. Waveband calibrations at 531, 547, and 555 nm were below R2 = 0.50, and therefore were not considered further. MODIS Rrs, from the standard atmospheric correction, followed nearly identical spectral shapes to the in situ HyperSAS Rrs, but were on average 0.002 ± 0.0004 sr−1 less. A satellite to in situ validation match-up window of ≤1 hour was selected with an R2 = 0.82 and root mean square error RMSE = 1.79 at 412 nm. An in situ water quality mooring demonstrated that the overall response and range of MODIS ag412 were similar, with relative mean error from –32% to 42%. The advantage to managers was synoptic coverage across multiple estuaries and the ability to provide estimates of derived water quality parameters between the water quality assessment programme sample collection periods, which could offer more holistic assessment.

A controlled laboratory study was conducted to measure the dispersion effectiveness of Corexit 9500 on 23 different crude oils. This study was a part of a larger project initiated by the Bureau of Safety and Environmental Enforcement (BSEE) testing 20 oils to compare the predictive value of laboratory dispersant effectiveness tests with their larger scale test conducted at Ohmsett, BSEE’s national oil spill response test facility located in Leonardo, NJ. The test used in this study was the Baffled Flask Test (BFT), which is planned for adoption as EPA’s official testing protocol for listing commercial dispersant products on the National Contingency Plan Product Schedule, replacing the current Swirling Flask Test (SFT) [1]. In addition, the results of 3 additional oils, the 2 used in the SFT and BFT as currently written plus another reference oil, are presented. The temperature used for the tests was 15°C, to match the temperature used at Ohmsett. The dispersion effectiveness ranged from 3.4% to 93%. The BFT is a laboratory test with results that are inversely correlated with oil viscosity and therefore has predictive value in the decision to use a dispersant in the event of a spill.

To better understand the impacts of Corexit 9500 on the structure and activity levels of hydrocarbon-degrading microbial communities, we analyzed next-generation 16S rRNA gene sequencing libraries of hydrocarbon enrichments grown at 5 and 25°C using both DNA and RNA extracts as the sequencing templates. Oil biodegradation patterns in both 5 and 25°C enrichments were consistent with those reported in the literature (i.e., aliphatics were degraded faster than aromatics). Slight increases in biodegradation were observed in the presence of Corexit at both temperatures. Differences in community structure were observed between treatment conditions in the DNA-based libraries. The 25°C consortia were dominated by Vibrio , Idiomarina , Marinobacter , Alcanivorax , and Thalassospira species, while the 5°C consortia were dominated by several species of the genera Flavobacterium , Alcanivorax , and Oleispira . Most of these genera have been linked to hydrocarbon degradation and have been observed after oil spills. Colwellia and Cycloclasticus , known aromatic degraders, were also found in these enrichments. The addition of Corexit did not have an effect on the active bacterial community structure of the 5°C consortia, while at 25°C, a decrease in the relative abundance of Marinobacter was observed. At 25°C, Thalassospira , Marinobacter , and Idiomarina were present at higher relative abundances in the RNA than DNA libraries, suggesting that they were active in degradation. Similarly, Oleispira was greatly stimulated by the addition of oil at 5°C. IMPORTANCE While dispersants such as Corexit 9500 can be used to treat oil spills, there is still debate on the effectiveness on enhancing oil biodegradation and its potential toxic effect on oil-degrading microbial communities. The results of this study provide some insights on the microbial dynamics of hydrocarbon-degrading bacterial populations in the presence of Corexit 9500. Operational taxonomic unit (OTU) analyses indicated that several OTUs were inhibited by the addition of Corexit. Conversely, a number of OTUs were stimulated by the addition of the dispersant, many of which were identified as known hydrocarbon-degrading bacteria. The results highlight the value of using RNA-based methods to further understand the impact of dispersant on the overall activity of different hydrocarbon-degrading bacterial groups.

The surface oil burns conducted by the U.S. Coast Guard from April to July 2010 during the Deepwater Horizon disaster in the Gulf of Mexico were simulated by small scale burns to characterize the pollutants, determine emission factors, and gather particulate matter for subsequent toxicity testing. A representative crude oil was burned in ocean-salinity seawater, and emissions were collected from the plume by means of a crane-suspended sampling platform. Emissions included particulate matter, aromatic hydrocarbons, polychlorinated dibenzodioxins/dibenzofurans, elements, and others, the sum of which accounted for over 92% by mass of the combustion products. The unburned oil mass was 29% of the original crude oil mass, significantly higher than typically reported. Analysis of alkanes, elements, and PAHs in the floating residual oil and water accounted for over 51% of the gathered mass. These emission factors, along with toxicity data, will be important toward examining impacts of future spill burning operations.

In situ fluorometers were deployed during the Deepwater Horizon (DWH) Gulf of Mexico oil spill to track the subsea oil plume. Uncertainties regarding instrument specifications and capabilities necessitated performance testing of sensors exposed to simulated, dispersed oil plumes. Dynamic ranges of the Chelsea Technologies Group AQUAtracka, Turner Designs Cyclops, Satlantic SUNA and WET Labs, Inc. ECO, exposed to fresh and artificially weathered crude oil, were determined. Sensors were standardized against known oil volumes and total petroleum hydrocarbons and benzene-toluene-ethylbenzene-xylene measurements-both collected during spills, providing oil estimates during wave tank dilution experiments. All sensors estimated oil concentrations down to 300 ppb oil, refuting previous reports. Sensor performance results assist interpretation of DWH oil spill data and formulating future protocols.

Sustainable practices require a long-term commitment to creating solutions to environmental, social, and economic issues. The most direct way to ensure that management practices achieve sustainability is to monitor the environment. Remote sensing technology has the potential to accelerate the engagement of communities and managers in the implementation and performance of best management practices. Over the last few decades, satellite technology has allowed measurements on a global scale over long time periods, and is now proving useful in coastal waters, estuaries, lakes, and reservoirs, which are relevant to water quality managers. Comprehensive water quality climate data records have the potential to provide rapid water quality assessments, thus providing new and enhanced decision analysis methodologies and improved temporal/spatial diagnostics. To best realize the full application potential of these emerging technologies an open and effective dialogue is needed between scientists, policy makers, environmental managers, and stakeholders at the federal, state, and local levels. Results from an internal US Environmental Protection Agency qualitative survey were used to determine perceptions regarding the use of satellite remote sensing for monitoring water quality. The goal of the survey was to begin understanding why management decisions do not typically rely on satellite-derived water quality products.

The increasing level of commercial marine activity in high latitudes creates an ever growing risk of oil spills. Even in logistically accessible, ice-free oceans, characterizing the extent and nature of a spill can be challenging as highlighted by the Deepwater Horizon incident. We propose to develop an AUV-based approach inspired by an existing small, long-range system, called the Tethys Long-Range AUV (LRAUV), in order to support the Arctic Doman Awareness Center (ADAC) for spill preparedness.

This study was aimed at testing the applicability of modified Weber number scaling with Alaska North Slope (ANS) crude oil, and developing a Reynolds number scaling approach for oil droplet size prediction for high viscosity oils. Dispersant to oil ratio and empirical coefficients were also quantified. Finally, a two-step Rosin-Rammler scheme was introduced for the determination of droplet size distribution. This new approach appeared more advantageous in avoiding the inconsistency in interfacial tension measurements, and consequently delivered concise droplet size prediction. Calculated and observed data correlated well based on Reynolds number scaling. The relation indicated that chemical dispersant played an important role in reducing the droplet size of ANS under different seasonal conditions. The proposed Reynolds number scaling and two-step Rosin-Rammler approaches provide a concise, reliable way to predict droplet size distribution, supporting decision making in chemical dispersant application during an offshore oil spill.

While the spatial heterogeneity of many aquatic ecosystems is acknowledged, rivers are often mistakenly described as homogenous and well-mixed. The collection and visualization of attributes like water quality is key to our perception and management of these ecosystems. The assumption of homogeneity can lead to the conclusion that data collection from discrete, discontinuous points in space or time provide a comprehensive estimate of condition. To counter this perception, we combined high-density data collection with spatial interpolation techniques to created two-dimensional maps of water quality. Maps of four riverine transitions and habitats – wetland to urban, river to reservoir, river to estuary and a groundwater intrusion – were constructed from the continuous data. The examples provided show that the most basic water quality parameters - temperature, conductivity, salinity, turbidity, and chlorophyll florescence - are heterogeneous at spatial scales smaller than those captured by common point sampling statistical strategies. The 2-dimensional, interpolation-based maps of the Hillsborough River (Tampa, FL) show significant influences of a variety of geographic features including tributary confluences, submarine groundwater inflow, and riparian interfaces. We conclude that many sampling strategies do not account for the type of patchy heterogeneity observed. The integration of existing in-situ sensors, inexpensive autonomous sampling platforms, and geospatial mapping techniques provides high resolution visualization that can adds a more comprehensive geographic perspective needed for environmental monitoring and assessment programs.

Human activities on land increase nutrient loads to coastal waters, which can increase phytoplankton production and biomass and associated ecological impacts. Numeric nutrient water quality standards are needed to protect coastal waters from eutrophication impacts. The Environmental Protection Agency determined that numeric nutrient criteria were necessary to protect designated uses of Florida's waters. The objective of this study was to evaluate a reference condition approach for developing numeric water quality criteria for coastal waters, using data from Florida. Florida's coastal waters have not been monitored comprehensively via field sampling to support numeric criteria development. However, satellite remote sensing had the potential to provide adequate data. Spatial and temporal measures of SeaWiFS OC4 chlorophyll-a (Chl(RS)-a, mg m(-3)) were resolved across Florida's coastal waters between 1997 and 2010 and compared with in situ measurements. Statistical distributions of Chl(RS)-a were evaluated to determine a quantitative reference baseline. A binomial approach was implemented to consider how new data could be assessed against the criteria. The proposed satellite remote sensing approach to derive numeric criteria may be generally applicable to other coastal waters.

Absorption and fluorescence of colored dissolved organic matter (CDOM) and concentrations of dissolved organic carbon (DOC), chlorophyll and total suspended solids in Tampa Bay and its adjacent rivers were examined in June and October of 2004. Except in Old Tampa Bay (OTB), the spatial distribution of CDOM showed a conservative relationship with salinity in June, 2004 (aCDOM(400)= −0.19×salinity+6.78, R 2 =0.98, n=17, salinity range=1.1–32.5) with little variations in absorption spectral slope and fluorescence efficiency. This indicates that CDOM distribution was dominated by mixing. In October, 2004, CDOM distribution was nonconservative with an average absorption coefficient (aCDOM(400), ∼7.76 m −1 ) about seven times higher than that in June (∼1.11 m −1 ). The nonconservative behavior was caused largely by CDOM removal at intermediate salinities (e.g., aCDOM(400) removal N15% at salinity ∼13.0), which likely resulted from photobleaching due to stronger stratification. The spatial and seasonal distributions of CDOM in Tampa Bay showed that the two largest rivers, the Alafia River (AR) and Hillsborough River (HR) were dominant CDOM sources to most of the bay. In OTB, however, CDOM showed distinctive differences: lower absorption coefficient, higher absorption spectral slopes, and lower ratios of CDOM absorption to DOC and higher fluorescence efficiency. These differences may have stemmed from (1) changes in CDOM composition by more intensive photobleaching due to the longer residence time of water mass in OTB; (2) other sources of CDOM than the HR/AR inputs, such as local creeks, streams, groundwater, and/or bottom re-suspension. Average CDOM absorption in Tampa Bay at 443 nm, aCDOM(443), was about five times higher in June and about ten times higher in October than phytoplankton pigment absorption, aph(443), indicating that blue light attenuation in the water column was dominated by CDOM rather than by phytoplankton absorption throughout the year. © 2007 Elsevier B.V. All rights reserved.

Variations in the concentration and inherent optical properties of colored dissolved organic matter (CDOM) in river-dominated margins provide information on the cycling of carbon and its chemical composition. Large-scale temporal and spatial variability in CDOM concentration and optical properties were observed in the Northern Gulf of Mexico in June of 2000 and April of 2001. Terrestrial CDOM from the Mississippi and Atchafalaya Rivers dominates the region. Although the primary factor controlling CDOM in this region is the quantity of fresh water runoff, strong regional variability in fresh water sources also plays a major role. Physical complexity due to changes in circulation patterns, volume of river flow and multiple river sources makes observation of biological and photochemical effects challenging in this region. We have used two approaches to distinguish between source and transformation effects: mixing models, which include the concentration and inherent optical properties of CDOM from discrete samples, and high-resolution three-dimensional mapping of multi-spectral fluorescence.

Chromophoric dissolved organic matter (CDOM) in the Mississippi plume region may have several distinct sources: riverine (terrestrial soils), wetland (terrestrial plants), biological production (phytoplankton, zooplankton, microbial), and sediments. Complex mixing, photodegradation, and biological processes make differentiation of the specific sources of CDOM difficult. Using a combination of high resolution in situ observations on an undulating vehicle, the ECOShuttle, a pumping system mounted on the vehicle, and detailed chemical and biological analyses of discrete samples allowed us to characterize two specific sources of CDOM in the Louisiana Bight: the river water constrained in the upper 12 m of the Mississippi River plume and several subsurface layers of CDOM below the plume. The subsurface CDOM maxima were coincident with steep pycnoclines and sometimes with maxima in chlorophyll a fluorescence. Both sources were actively supplying CDOM to the same location by entirely different processes. The subsurface CDOM was more biologically labile and photochemically refractory than the surface CDOM. Optical properties were also different with a relatively higher protein fluorescence and a lower spectral slope coefficient in the subsurface CDOM. The geographical extent of the two sources was determined by threedimensional mapping of the area, and due to the relatively calm conditions in the summer of 2000, thin layers of CDOM produced in the subsurface were observed throughout the region. While riverine inputs dominated the distribution of CDOM in surface waters

Alterations in colored dissolved organic matter (CDOM) characteristics were examined for an extensive fluorescence data set generated by excitation emission matrix spectroscopy (EEMS). Principal component analysis (PCA) was used to assess changes in fluorescence bandwidth and wavelength shifts of entire peak regions, enhancing previous CDOM characterization that was based on changes observed at a few excitation and emission wavelength pairs. Variability within the data set is expressed as a series of linear terms, which can be used to quantitatively evaluate changes in CDOM fluorescence within the perspective of a single cruise or a large geographic region. In this paper we will present PCA results from a comprehensive fluorescence data set examining seasonal and regional CDOM variability within the Gulf of Mexico.

The development of multispectral in situ fluorescence instruments greatly enhances the study of the optical properties of Colored Organic Matter (COM). Here, we tested the inter-instrument variability of three WetLabs, Inc. SAFIres using quinine sulfate standards. As with any fluorometer, intensity and spectral biases in fluorescence output due to properties of the SAFIre's optical components necessitate corrections. Low response of the instrument to quinine sulfate and lack of an excitation/emission channel at the fluorescence maximum of this standard precluded direct spectral calibration. Calibrations conducted using seawater as a secondary standard provided an acceptable alternative. The field performance of the SAFIre from two experiments is presented here. Time series contour plots show that the instrument has the ability to detect small differences in COM optical properties, and observed fluorescence emission ratios are indicative of changes in sources of the material over the course of the study. The SAFIre was found to extend multispectral measurements to include high spatial and high temporal resolution.

We performed multispectral in-situ fluorescence measurement of colored dissolved organic matter and chlorophyll in surface water of the West Florida Shelf using West Labs Spectral absorption and Fluorescence Instrument (SAFIre). Continuous measurements underway allowed us to simultaneously map the dispersion of riverine organic material and chlorophyll on the shelf. By using two fluorescence emission ratios we were able to differentiate between riverine and marine CDOM. Our data also showed unusually high concentrations of CDOM offshore. These were attributed to an intrusion of the Mississippi River Plume. We performed limited comparisons between in-situ chlorophyll concentrations measured with SAFIre and chlorophyll values obtained from SeaWiFS satellite data using OC4 and MODIS algorithm. Our results show that, although both algorithms overestimated chlorophyll, MODIS performed better than OC4, particularly in areas with high CDOM concentrations. Analysis of the relationship between chlorophyll and CDOM concentrations within the study area showed regional variability causes by differences in river source.

Chromophoric dissolved organic matter (CDOM) spectral absorption, dissolved organic carbon (DOC) concentration, and the particulate fraction of inorganic (PIM) and organic matter (POM) were measured in Louisiana coastal waters at Vermilion, Atchafalaya, Terrebonne, Barataria, and Mississippi River locations, in 2007-2008. The range of CDOM was 0.092 m⁻¹ at Barataria in June 2008 to 11.225 m⁻¹ at Mississippi in February 2008. An indicator of organic matter quality was predicted by the spectral slope of absorption coefficients from 350 to 412nm which was between 0.0087 m⁻¹ at Mississippi in May 2008 and 0.0261 m⁻¹ at Barataria in June 2008. CDOM was the dominant component of light attenuation at Terrebonne and Barataria. Detritus and CDOM were the primary components of light attenuation at Vermilion, Atchafalaya, and Mississippi. DOC ranged between 65 and 1235 μM. PIM ranged between 1.1 and 426.3 mg L⁻¹ and POM was between 0.3 and 49.6 mg L⁻¹.

[1] Colored Dissolved Organic Matter (CDOM) distribution and signatures provide vital information about the amount and composition of organic material in aquatic environments. This information is critical for deciphering the sources and biogeochemical pathways of organic carbon, and thus vital to the understanding of carbon cycling and budgets. Waters of the West Florida Shelf are heavily influenced by many river systems on Florida's Gulf Coast that, to the first order, control CDOM distributions on the shelf. Three storm events during 2004 and 2005 (Hurricane Charley, Hurricane Wilma, and a Winter Storm) profoundly altered the typical distribution of CDOM fluorescence and absorption properties on the Southern West Florida Shelf. Seasonal surveys revealed that changes in the underwater light field as a result of major hurricanes and resuspension events are linked closely with a number of factors prior to a storm's passing such as the presence of persistent blooms, rainfall and discharge. Additionally, storm track and wind direction were found to play a significant role in CDOM signatures.

[1] We have combined a circulation model with one of colored dissolved organic matter (CDOM) photolysis to describe the fate of terrestrial CDOM on the West Florida shelf (WFS). Our results for summer 1998 suggest that a near shore plume of CDOM became entrained in a coastal jet extending south from the Suwannee River (Big Bend) region of the WFS towards the Florida Keys—a feature also evident in satellite ocean color imagery. The coupled models suggest that photochemical losses of CDOM were significant, but provided only a minimal nitrogen source for phytoplankton growth on the WFS.

In situ fluorometers were deployed during the Deepwater Horizon (DWH) Gulf of Mexico oil spill to provide critical measurements for tracking the subsea oil plume. In the wake of the spill, uncertainties regarding instrument specifications, capabilities and reliability necessitated performance testing of sensors (commonly used during spill response) exposed to simulated, dispersed oil plumes. Moreover, concerns on the applicability of laboratory calibrations (at high concentrations and insufficient mixing energies) to field conditions and on sensor reliability to detect dispersed oil persist. To address these uncertainties the performance of select commercially-available sensors (from Chelsea Technologies Group, Satlantic, Turner Designs, WetLabs Inc) was evaluated using a wave tank facility at the Bedford Institute of Oceanography in Halifax, Nova Scotia. Breaking waves were generated within the tank to simulate mixing energies and achieve dispersant effectiveness observed in the field. Presented here are the results of the sensors exposed to chemically-dispersed MC252 crude oil using Corexit 9500, DOR=1:20. Stepwise additions of dispersed oil (0.3 – 12 ppm) to the tank were used to establish linearity. Model 1 linear least squares regressions were calculated and applied to sensor data during validation experiments to simulate dilution of an oil plume. Dynamic ranges of the sensors, exposed to fresh and artificially weathered crude oil, were determined. Sensors were standardized against known oil volumes and measured Total Petroleum Hydrocarbons (TPH) and Benzene-Toluene-Ethylbenzene-Xylene (BTEX) values – both collected during spills, providing oil estimates during dilution experiments. Results were validated against particle size data (Sequoia LISST). All sensors estimated oil concentrations down to 300 ppb oil, refuting previous reports. Low percent differences and absolute errors between chemistry and sensor results were metrics to evaluate performance. Discussed will be the application of this vicarious calibration approach as a means to calibrate the DWH fine-scale fluorescence data into oil concentrations. This allows for filling in coarse-scale field chemistry data, improved assessment of DWH spill measurements mined from the NOAA NODC, and understanding the fate and transport of the DWH oil plume.