Crude oils are some of the most complex and diverse organic mixtures found in nature. They contain thousands of different compounds belonging to several compound classes, with the main ones being ...hydrocarbons and their heteroatom (N, S, and O)-containing analogs, called non-hydrocarbons. In general, all crude oils contain the same types of chemical structures, but these compounds can be in highly variable proportions in crude oils drawn from different reservoir conditions and locations. Both the types of compounds and their respective quantities change rapidly once the crude oil is spilled into the environment, making the circumstances associated with every spill unique. In general, smaller and lower molecular weight oil compounds are more susceptible to processes such as evaporation, dissolution, and biodegradation, while the heavier, more hydrophobic compounds tend to adhere to living organisms or particulates and persist. The presence of certain compounds, such as PAHs (polycyclic aromatic hydrocarbons), also determines the acute and chronic toxicity of the spilled oil. Natural processes can degrade virtually all compounds in crude oils, with aerobic oxidation proceeding much faster than anaerobic degradation, although not all crude oil components are degraded with the same speed. The environmental fate and effects of crude oil degraded by biodegradation and photooxidation are yet to be fully determined. Due to the submarine and offshore setting of the Macondo well blowout, components of the spilled oil were distributed throughout the marine environment—water column, sediments, surface waters, and the coast. The light and nonviscous nature of Macondo crude oil favored its removal through natural degradation, evaporation, dissolution, and dispersal processes. In spite of the unprecedented quantities of oil that spilled, the final fate and effects of the oil, the more recalcitrant fractions of Macondo oil, and the oil weathering products have not been totally elucidated. Responders with knowledge of the physical properties of the Macondo oil executed their preplanned response efforts and kept a majority of the oil from reaching the more sensitive coastal areas.
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Approximately 4.9 million barrels of crude oil and gas were released into the Gulf of Mexico (GoM) from April to July 2010 during the Deepwater Horizon (DWH) spill. This resulted in the possible ...contamination of marine organisms with polycyclic aromatic hydrocarbons (PAHs), USEPA identified constituents of concern. To determine the impact of the DWH oil spill, Gulf menhaden (Brevoortia patronus), a commercially harvested and significant trophic grazing species, was sampled from two Louisiana coastal regions between the years 2011–2013. Tissue extraction and GC/MS analysis demonstrated measurable concentrations of PAH within menhaden. Analysis yielded total PAHs, carcinogenic equivalents (BaP-TEQ), and mutagenic equivalents (BaP-MEQ) which provided an initial toxic potential assessment of this GoM Fishery. Gulf menhaden contained less total PAH concentrations in 2012 and significantly less in 2013 as compared to 2011 (p < 0.05) ranging from 7 ug/g tissue dry weight to 3 ng/g tissue dry weight. Carcinogenic and mutagenic PAHs were also significantly reduced (p < 0.05) over the three year period. The reduction of total PAH concentrations and the reduction of BaP-TEQs and MEQs between 2011 and 2013 indicates a diminished input of new source PAHs along with a reduction of carcinogenic and mutagenic PAHs in menhaden populations. The use of Gulf menhaden was successful in determining the acute toxic potential of PAHs contaminating the GoM in the years directly following the DWH spill event.
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•Gulf menhaden were used to evaluate PAH concentrations in the Gulf of Mexico.•PAHs were extracted using a modified MSPD method.•PAHs were converted to BaP-TEQs and BaP-MEQs for better quantification of data.•PAH concentrations along with BaP-TEQs and MEQs decreased significantly by 2013.•Gulf menhaden are a useful species for acute impact assessment of oil spill events.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
We measured the temporal and spatial trajectory of oiling from the April, 2010, Deepwater Horizon oil spill in water from Louisiana's continental shelf, the estuarine waters of Barataria Bay, and in ...coastal marsh sediments. The concentrations of 28 target alkanes and 43 target polycyclic aromatic hydrocarbons were determined in water samples collected on 10 offshore cruises, in 19 water samples collected monthly one km offshore at 13 inshore stations in 2010 and 2013, and in 16–60 surficial marsh sediment samples collected on each of 26 trips. The concentration of total aromatics in offshore waters peaked in late summer, 2010, at 100 times above the May, 2010 values, which were already slightly contaminated. There were no differences in surface or bottom water samples. The concentration of total aromatics declined at a rate of 73% y−1 to 1/1000th of the May 2010 values by summer 2016. The concentrations inside the estuary were proportional to those one km offshore, but were 10–30% lower. The oil concentrations in sediments were initially different at 1 and 10 m distance into the marsh, but became equal after 2 years. Thus, the distinction between oiled and unoiled sites became blurred, if not non-existent then, and oiling had spread over an area wider than was visible initially. The concentrations of oil in sediments were 100–1000 times above the May 2010 values, and dropped to 10 times higher after 8 years, thereafter, demonstrating a long-term contamination by oil or oil residues that will remain for decades. The chemical signature of the oil residues offshore compared to in the marsh reflects the more aerobic offshore conditions and water-soluble tendencies of the dissolved components, whereas the anaerobic marsh sediments will retain the heavier molecular components for a long time, and have a consequential effect on the ecosystems.
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•Oil concentrations on shelf and in marsh were followed for 8 years post DWH oil spill.•Targeted aromatic concentrations peaked on shelf at 100 times above initial values.•Targeted aromatics concentrations in offshore water declined after 2010 at 73% y−1.•Marsh sediment concentrations remain at 10 times higher than pre-spill conditions.•Anaerobic soils retained heavier oil molecules that may have consequential ecological effect.
Measured concentration of alkanes and aromatics in shelf waters and marsh sediments over 8 years after the Deepwater Horizon oil spill. Molecular transformations described.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
•We measured oil in wetlands before and after the 2010 Macondo oil spill disaster.•Alkanes and PAH concentrations were 604 and 186 X the baseline values, respectively.•Oil was found at least 100m ...inland from the shoreline and without much attenuation.•Alkanes may be at baseline concentrations by 2015, but take many decades for PAHs.
We measured the concentration of petroleum hydrocarbons in 405 wetland sediment samples immediately before the April 2010 Deepwater Horizon disaster led to their broad-scale oiling, and on nine trips afterwards. The average concentrations of alkanes and PAHs were 604 and 186 times the pre-spill baseline values, respectively. Oil was distributed with some attenuation up to 100m inland from the shoreline for alkanes, but increased for aromatics, and was not well-circumscribed by the rapid shoreline assessments (a.k.a. SCAT) of relative oiling. The concentrations of target alkanes and PAHs in June 2013 were about 1% and 5%, respectively, of the February 2011 concentrations, but remained at 3.7 and 33 times higher, respectively, than in May 2010. A recovery to baseline conditions suggests that the concentration of alkanes may be near baseline values by the end of 2015, but that it may take decades for the PAH concentrations to be that low.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
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•Oil source-fingerprinting (OSF) identified Macondo-252 oil in coastal marshes.•OSF supports polarimetric SAR remote sensing detection of oil in interior marshes.•Shoreline and ...interior marsh sediments were collected a year after the oil spill.•Diagnostic ratio analyses (DRA) quantified categories of oil sediment occurrence.•Similarity analyses extended DRA oil sediment categories to non-conclusive samples.
Polarimetric synthetic aperture radar (PolSAR) data exhibited dramatic, spatially extensive changes from June 2009 to June 2010 in Barataria Bay, Louisiana. To determine whether these changes were associated with the Deepwater Horizon (DWH) oil spill, twenty-nine sediment samples were collected in 2011 from shoreline and nearshore–interior coastal marsh locations where oil was not observed visually or with optical sensors during the spill. Oil source-fingerprinting and polytopic vector analysis were used to link DWH oil to PolSAR changes. Our results prove that DWH oil extended beyond shorelines and confirm the association between presence of DWH oil and PolSAR change. These results show that the DWH oil spill probably affected much more of the southeastern Louisiana marshland than originally concluded from ground and aerial surveys and verify that PolSAR is a powerful tool for tracking oil intrusion into marshes with high probability even where contamination is not visible from above the canopy.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
During the 2010 Deepwater Horizon oil well blowout in the Northern Gulf of Mexico (GoM), the application of 6.97 million litres of chemical dispersants was used at the well-head and on the sea ...surface to promote oil degradation and weathering of the Mississippi Canyon 252 (MC252) crude oil. Chemical dispersants encourage microbial degradation by increasing the surface area of the spilled oil, which also increases its bioavailability. However, the net beneficial effects of using chemical dispersants on spilled oil and their effects on weathering are not completely elucidated in contemporary literature. The use of simulated environmental conditions in replicate laboratory microcosm weathering experiments were employed to study the weathering of oil and the effects of dispersants on oil weathering. Fresh MC252 oil was evaporatively weathered 40% by-weight to approximate the composition of oil seen in surface slicks during the 2010 spill. This surface oil was then well mixed with two types of seawater, autoclaved artificial seawater, the abiotic control, and Gulf of Mexico seawater, the biotic experiment. Four different weathering combinations were tested: 10 mg of oil mixed in 150 ml artificial seawater (OAS) or natural (i.e., GoM) seawater (ON) and 10 mg of oil with dispersant mixed with 150 ml of artificial seawater (OASD) or natural (i.e., GoM) seawater (OND). For the treatments with dispersant (OASD and OND), the dispersant-to-oil ratio (DoR) was 1:20. The experiment was carried out over 28 days with replicates that were sacrificed on Days 0, 0.5, 3, 7, 14, 21 and 28. For the OAS and OASD treatments, abiotic weathering (i.e., evaporation) dominated the weathering process. However, the ON and OND treatments showed a dramatic and rapid decrease in total concentrations of both alkanes and aromatics with biodegradation dominating the weathering process. Further, there were no identifiable differences in the observed weathering patterns between microcosms using oil or oil treated with dispersant. In the biotic weathering microcosms, the relative degree of individual polycyclic aromatic hydrocarbon (PAH) depletion decreases with an increase in rings and within a homolog series (increased alkylation). The n-C17/pristane and n-C18/phytane ratios rapidly decreased compared to the abiotic weathering experiments. The C2-dibenzothiophenes (DBT)/C2-phenanthrenes (D2/P2) and C3-DBTs/C3-phenanthrenes (D3/P3) ratios initially remained constant during the early stages of weathering and then increased with time showing preferential weathering of the sulfur containing compounds compared to similar sized PAH compounds. These ratios in the abiotic microcosms remained constant over 28 days. Additionally, twenty-four quantitative MC252 oil biomarker ratios were evaluated to determine if their usefulness as oil source-fingerprinting tools were compromised after significant weathering and dispersant augmentation.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
A new adaptation based on matrix solid phase dispersion of tissue for the subsequent isolation of polycyclic aromatic hydrocarbons was developed and used for extractions of Gulf menhaden caught ...during the summer of 2011. Many Matrix Solid Phase Dispersion (MSPD) methods require specific cartridges and other clean-up materials in order to achieve proper extraction. For this study, the tissues were lyophilized prior to applying the adapted MSPD method allowing for a much more complete homogenization with the C18 silica. The tissue was spiked with phenanthrene d10 as a surrogate as a measure of PAH recovery prior to the lyophilisation process to determine if any target compounds were lost and prior to sonication as per the finalized adaptation procedure to determine method efficiency. This technique used C18 silica in a 1 : 1 ratio as the primary homogenizing material for the menhaden tissue matrix and was eluted with dichloromethane (DCM) until visibly clear. The overall study mean recovery was 88 % ± 5 % with method detection limits between 0.4 ng/g and 4.4 ng/g tissue dry weight. This adapted protocol has been used exclusively on the analysis of high lipid content fish stocks affected by dispersed and weathered oil from the BP Horizon incident.
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FZAB, GIS, IJS, IZUM, KILJ, NLZOH, NUK, OILJ, PILJ, PNG, SAZU, SBCE, SBMB, UL, UM, UPUK
Following oil spills such as the Deepwater Horizon accident (DWH), contamination of seafood resources and possible increased health risks attributable to consumption of seafood in spill areas are ...major concerns. In this study, locally harvested finfish and shrimp were collected from research participants in southeast Louisiana and analyzed for polycyclic aromatic hydrocarbons (PAHs). PAHs are some of the most important chemicals of concern regarding oil‐spill‐contaminated seafood resources during and following oil spills. Some PAHs are considered carcinogens for risk assessment purposes, and currently, seven of these can be combined in lifetime cancer risk assessments using EPA approaches. Most PAHs were not detected in these samples (minimum detection limits ranged from 1.2 to 2.1 PPB) and of those that were detected, they were generally below 10 PPB. The pattern of detected PAHs suggested that the source of these chemicals in these seafood samples was not a result of direct contact with crude oil. Lifetime cancer risks were assessed using conservative assumptions and models in a probabilistic framework for the seven carcinogenic PAHs. Lifetime health risks modeled using this framework did not exceed a 1/10,000 cancer risk threshold. Conservative, health‐protective deterministic estimates of the levels of concern for PAH chemical concentration and seafood intake rates were above the concentrations and intake rates modeled under this probabilistic framework. Taken together, consumption of finfish and shrimp harvested from southeast Louisiana following the DWH does not pose unacceptable lifetime cancer risks from these seven carcinogenic PAHs even for the heaviest possible consumers.
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BFBNIB, FSPLJ, FZAB, GIS, IJS, IZUM, KILJ, NLZOH, NUK, OILJ, PILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Oil source-fingerprinting is an environmental forensics technique that uses analytical chemistry to determine the origin of oil residues in environmental samples by comparison to a known or suspected ...source oil. Currently, the only standardized method for oil source fingerprinting is a qualitative approach that is very effective in almost every oil spill response situation. However, the need for quantitative oil source-fingerprinting methods to complement the qualitative determinations is extremely desired. The research herein aims to utilize data generated by gas chromatography/mass spectrometry (GC/MS) methodologies to test two different quantitative techniques: diagnostic biomarker ratio analysis and chemometrics.The most common crude oil constituents used for oil source-fingerprinting are the oil biomarker compounds. Oil biomarkers are polycyclic aliphatic hydrocarbon molecules typically resistant to environmental weathering (i.e., biological and physiochemical transformations). They are universal in crude oils and most petroleum products, and impart unique ratios in oils of different maturities and geographic sources. Diagnostic biomarker ratio analysis will be used to establish a suite of diagnostic biomarker ratios with statistical limitations that can differentiate oil from the Deepwater Horizon oil spill, or Macondo 252 (MC252) oil, from other South Louisiana crude oils. This technique is not limited to MC252 oil. Diagnostic ratios can be determined and tested for any source oil.Current published research has documented weathering of several of the biomarker compounds used for oil source-fingerprinting. Any weathering of MC252 oil residues in the environment will adversely affect the diagnostic biomarker ratio analysis. Therefore, a more advanced quantitative technique, chemometrics, will use pattern recognition algorithms to determine the innate similarity of environmental oil residues to MC252 oil.
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