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.

Development of an offshore response guidance tool for determining the impact of SSDI on released gas and benzene from artificial subsea oil well blowout simulations.

We present an analysis of 2225 simulations of artificial oil well blowouts in nearshore and offshore waters of Newfoundland, Canada. In the simulations, we coupled the VDROP-J and TAMOC models to simulate the fate and transport of oil and gas from the release to the sea surface. Simulations were conducted with and without subsea dispersant injection. We analyzed the simulation database to quantify the mass fraction of oil and gas that surfaces, the mass fraction of released benzene that surfaces, and the horizontal offset to the surfacing zone. These data are also synthesized to yield empirical correlations to predict these output metrics from key input parameters. These correlations are summarized in an excel spreadsheet that allows rapid evaluation of spill dynamics with minimal initial knowledge of spill details. We call this tool an offshore response guidance table, which allows exploration of spill dynamics under diverse spill and response options.

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.

Biodegradation of Crude Oil and Corexit 9500 in Arctic Seawater.

The need to understand the biodegradation of oil and chemical dispersants in Arctic marine environments is increasing alongside growth in oil exploration and transport in the region. We chemically quantified biodegradation and abiotic losses of crude oil and Corexit 9500, when present separately, in incubations of Arctic seawater and identified microorganisms potentially involved in biodegradation of these substrates based on shifts in bacterial community structure (16S rRNA genes) and abundance of biodegradation genes (GeoChip 5.0 microarray). Incubations were performed over 28-day time courses using surface seawater collected from near-shore and offshore locations in the Chukchi Sea. Within 28 days, the indigenous microbial community biodegraded 36% (k = 0.010 day-1) and 41% (k = 0.014 day-1) of oil and biodegraded 77% and 33% (k = 0.015 day-1) of the Corexit 9500 component dioctyl sodium sulfosuccinate (DOSS) in respective near-shore and offshore incubations. Non-ionic surfactants (Span 80, Tween 80, and Tween 85) present in Corexit 9500 were non-detectable by 28 days due to a combination of abiotic losses and biodegradation. Microorganisms utilized oil and Corexit 9500 as growth substrates during the incubation, with the Corexit 9500 stimulating more extensive growth than oil within 28 days. Taxa known to include oil-degrading bacteria (e.g., Oleispira, Polaribacter, and Colwellia) and some oil biodegradation genes (e.g., alkB, nagG, and pchCF) increased in relative abundance in response to both oil and Corexit 9500. These results increase our understanding of oil and dispersant biodegradation in the Arctic and suggest that some bacteria may be capable of biodegrading both oil and Corexit 9500.

Oil type and temperature dependent biodegradation dynamics - Combining chemical and microbial community data through multivariate analysis.

BACKGROUND: This study investigates a comparative multivariate approach for studying the biodegradation of chemically dispersed oil. The rationale for this approach lies in the inherent complexity of the data and challenges associated with comparing multiple experiments with inconsistent sampling points, with respect to inferring correlations and visualizing multiple datasets with numerous variables. We aim to identify novel correlations among microbial community composition, the chemical change of individual petroleum hydrocarbons, oil type and temperature by creating modelled datasets from inconsistent sampling time points. Four different incubation experiments were conducted with freshly collected Norwegian seawater and either Grane and Troll oil dispersed with Corexit 9500. Incubations were conducted at two different temperatures (5 °C and 13 °C) over a period of 64 days. RESULTS: PCA analysis of modelled chemical datasets and calculated half-lives revealed differences in the biodegradation of individual hydrocarbons among temperatures and oil types. At 5 °C, most n-alkanes biodegraded faster in heavy Grane oil compared to light Troll oil. PCA analysis of modelled microbial community datasets reveal differences between temperature and oil type, especially at low temperature. For both oils, Colwelliaceae and Oceanospirillaceae were more prominent in the colder incubation (5 °C) than the warmer (13 °C). Overall, Colwelliaceae, Oceanospirillaceae, Flavobacteriaceae, Rhodobacteraceae, Alteromonadaceae and Piscirickettsiaceae consistently dominated the microbial community at both temperatures and in both oil types. Other families known to include oil-degrading bacteria were also identified, such as Alcanivoracaceae, Methylophilaceae, Sphingomonadaceae and Erythrobacteraceae, but they were all present in dispersed oil incubations at a low abundance (< 1%). CONCLUSIONS: In the current study, our goal was to introduce a comparative multivariate approach for studying the biodegradation of dispersed oil, including curve-fitted models of datasets for a greater data resolution and comparability. By applying these approaches, we have shown how different temperatures and oil types influence the biodegradation of oil in incubations with inconsistent sampling points. Clustering analysis revealed further how temperature and oil type influence single compound depletion and microbial community composition. Finally, correlation analysis of degraders community, with single compound data, revealed complexity beneath usual abundance cut-offs used for microbial community data in biodegradation studies.

Differential Impacts of Willow and Mineral Fertilizer on Bacterial Communities and Biodegradation in Diesel Fuel Oil-Contaminated Soil.

Despite decades of research there is limited understanding of how vegetation impacts the ability of microbial communities to process organic contaminants in soil. Using a combination of traditional and molecular assays, we examined how phytoremediation with willow and/or fertilization affected the microbial community present and active in the transformation of diesel contaminants. In a pot study, willow had a significant role in structuring the total bacterial community and resulted in significant decreases in diesel range organics (DRO). However, stable isotope probing (SIP) indicated that fertilizer drove the differences seen in community structure and function. Finally, analysis of the total variance in both pot and SIP experiments indicated an interactive effect between willow and fertilizer on the bacterial communities. This study clearly demonstrates that a willow native to Alaska accelerates DRO degradation, and together with fertilizer, increases aromatic degradation by shifting microbial community structure and the identity of active naphthalene degraders.

Biodegradation of dispersed oil in Arctic seawater at -1°C.

As offshore oil and gas exploration expands in the Arctic, it is important to expand the scientific understanding of arctic ecology and environmental impact to mitigate operational risks. Understanding the fate of oil in arctic seawater is a key factor for consideration. Here we report the chemical loss due to the biodegradation of Alaska North Slope (ANS) crude oil that would occur in the water column following the successful dispersion of a surface oil slick. Primary biodegradation and mineralization were measured in mesocosms containing Arctic seawater collected from the Chukchi Sea, Alaska, incubated at -1°C. Indigenous microorganisms degraded both fresh and weathered oil, in both the presence and absence of Corexit 9500, with oil losses ranging from 46-61% and up to 11% mineralization over 60 days. When tested alone, 14% of 50 ppm Corexit 9500 was mineralized within 60 days. Our study reveals that microorganisms indigenous to Arctic seawater are capable of performing extensive biodegradation of chemically and physically dispersed oil at an environmentally relevant temperature (-1°C) without any additional nutrients.

The acute toxicity of chemically and physically dispersed crude oil to key Arctic species under Arctic conditions during the open water season.

The acute toxicity of physically and chemically dispersed crude oil and the dispersant Corexit 9500 were evaluated for key Arctic species. The copepod Calanus glacialis, juvenile Arctic cod (Boreogadus saida), and larval sculpin (Myoxocephalus sp.) were tested under conditions representative of the Beaufort and Chukchi Seas during the ice-free season. The toxicity of 3 water-accommodated fractions (WAF) of Alaska North Slope crude oil was examined with spiked, declining exposures. A dispersant-only test was conducted with the copepod C. glacialis. Each preparation with oil (WAF, breaking wave WAF [BWWAF], and chemically enhanced WAF [CEWAF]) produced distinct suites of hydrocarbon constituents; the total concentrations of oil were lowest in WAF and highest in CEWAF preparations. The relative sensitivity for the different species and age classes was similar within each WAF type. Median lethal concentration values based on total petroleum hydrocarbons ranged from 1.6 mg/L to 4.0 mg/L for WAF and BWWAF treatments and from 22 mg/L to 62 mg/L for CEWAF. For Corexit 9500 exposures, median lethal concentration values ranged from 17 mg/L to 50 mg/L. The differences in the relative toxicity among the accommodated fractions indicated that the majority of petroleum hydrocarbons in the CEWAF are in less acutely toxic forms than the components that dominate the WAF or BWWAF. Further evaluation showed that the parent polycyclic aromatic hydrocarbon compounds, specifically naphthalene, were highly correlated to acute toxicity.

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.