Minimizing risks from spilled oil to ecosystem services using influence diagrams: the Deepwater Horizon spill response

Decision science tools can be used in evaluating response options and making inferences on risks to ecosystem services (ES) from ecological disasters. Influence diagrams (IDs) are probabilistic networks that explicitly represent the decisions related to a problem and their influence on desired or undesired outcomes. To examine how IDs might be useful in probabilistic risk management for spill response efforts, an ID was constructed to display the potential interactions between exposure events and the trade-offs between costs and ES impacts from spilled oil and response decisions in the DWH spill event. Quantitative knowledge was not formally incorporated but an ID platform for doing this was examined. Probabilities were assigned for conditional relationships in the ID and scenarios examining the impact of different response actions on components of spilled oil were investigated in hypothetical scenarios. Given the structure of the ID, potential knowledge gaps included understanding of the movement of oil, the ecological risk of different spill-related stressors to key receptors (e.g., endangered species, fisheries), and the need for stakeholder valuation of the ES benefits that could be impacted by a spill. Framing the Deepwater Horizon problem domain in an ID conceptualized important variables and relationships that could be optimally accounted for in preparing and managing responses in future spills. These features of the developed IDs may assist in better investigating the uncertainty, costs, and the trade-offs if large-scale, deep ocean spills were to occur again.     

Analysis and modeling of airborne BTEX concentrations from the Deepwater Horizon oil spill

Concerns have been raised about whether the Deepwater Horizon oil spill cleanup workers experienced adverse health effects from exposure to airborne benzene, toluene, ethylbenzene, and xylene (BTEX) which volatilized from surfaced oil. Thus, we analyzed the nearly 20 000 BTEX measurements of breathing zone air samples of offshore cleanup workers taken during the six months following the incident (made publicly available by British Petroleum). The measurements indicate that 99% of the measurements taken prior to capping the well were 32-, 510-, 360-, and 77-fold lower than the U.S. Occupational Safety and Health Administration's Permissible Exposure Limits (PELs) for BTEX, respectively. BTEX measurements did not decrease appreciably during the three months after the well was capped. Moreover, the magnitudes of these data were similar to measurements from ships not involved in oil slick remediation, suggesting that the BTEX measurements were primarily due to engine exhaust rather than the oil slick. To supplement the data analysis, two modeling approaches were employed to estimate airborne BTEX concentrations under a variety of conditions (e.g., oil slick thickness, wind velocity). The modeling results corroborated that BTEX concentrations from the oil were well below PELs and that the oil was not the primary contributor to the measured BTEX.     

Impacts and recovery of the Deepwater Horizon oil spill on vegetation structure and function of coastal salt marshes in the northern Gulf of Mexico

We investigated the impacts of the Deepwater Horizon (DWH) oil spill on two dominant coastal saltmarsh plants, Spartina alterniflora and Juncus roemerianus, in the northern Gulf of Mexico and the processes controlling differential species-effects and recovery. Seven months after the Macondo MC 252 oil made landfall along the shoreline salt marshes of northern Barataria Bay, Louisiana, concentrations of total petroleum hydrocarbons in the surface 2 cm of heavily oiled marsh soils were as high as 510 mg g(-1). Heavy oiling caused almost complete mortality of both species. However, moderate oiling impacted Spartina less severely than Juncus and, relative to the reference marshes, had no significant effect on Spartina while significantly lowering live aboveground biomass and stem density of Juncus. A greenhouse mesocosm study supported field results and indicated that S. alterniflora was much more tolerant to shoot oil coverage than J. roemerianus. Spartina recovered from as much as 100% oil coverage of shoots in 7 months; however, Juncus recovered to a much lesser extent. Soil-oiling significantly affected both species. Severe impacts of the Macondo oil to coastal marsh vegetation most likely resulted from oil exposure of the shoots and oil contact on/in the marsh soil, as well as repeated oiling events.     

Aerostat sampling of PCDD/PCDF emissions from the Gulf oil spill in situ burns

Emissions from the in situ burning of oil in the Gulf of Mexico after the catastrophic failure of the Deepwater Horizon drilling platform were sampled for polychlorinated dibenzodioxins and polychlorinated dibenzofurans (PCDD/PCDF). A battery-operated instrument package was lofted into the plumes of 27 surface oil fires over a period of four days via a tethered aerostat to determine and characterize emissions of PCDD/PCDF. A single composite sample resulted in an emission factor of 2.0 ng toxic equivalency (TEQ) per kg of carbon burned, or 1.7 ng TEQ per kg of oil burned, determined by a carbon balance method. Carbon was measured as CO(2) plus particulate matter, the latter of which has an emission factor of 0.088 kg/kg carbon burned. The average plume concentration approximately 200-300 m from the fire and about 75-200 m above sea level was <0.0002 ng TEQ/m(3).     

CCN spectra, hygroscopicity, and droplet activation kinetics of secondary organic aerosol resulting from the 2010 Deepwater Horizon oil spill

Secondary organic aerosol (SOA) resulting from the oxidation of organic species emitted by the Deepwater Horizon oil spill were sampled during two survey flights conducted by a National Oceanic and Atmospheric Administration WP-3D aircraft in June 2010. A new technique for fast measurements of cloud condensation nuclei (CCN) supersaturation spectra called Scanning Flow CCN Analysis was deployed for the first time on an airborne platform. Retrieved CCN spectra show that most particles act as CCN above (0.3 ± 0.05)% supersaturation, which increased to (0.4 ± 0.1)% supersaturation for the most organic-rich aerosol sampled. The aerosol hygroscopicity parameter, κ, was inferred from both measurements of CCN activity and from humidified-particle light extinction, and varied from 0.05 to 0.10 within the emissions plumes. However, κ values were lower than expected from chemical composition measurements, indicating a degree of external mixing or size-dependent chemistry, which was reconciled assuming bimodal, size-dependent composition. The CCN droplet effective water uptake coefficient, γ(cond), was inferred from the data using a comprehensive instrument model, and no significant delay in droplet activation kinetics from the presence of organics was observed, despite a large fraction of hydrocarbon-like SOA present in the aerosol.     

Impact of the deepwater horizon oil spill on bioavailable polycyclic aromatic hydrocarbons in Gulf of Mexico coastal waters

An estimated 4.1 million barrels of oil and 2.1 million gallons of dispersants were released into the Gulf of Mexico during the Deepwater Horizon oil spill. There is a continued need for information about the impacts and long-term effects of the disaster on the Gulf of Mexico. The objectives of this study were to assess bioavailable polycyclic aromatic hydrocarbons (PAHs) in the coastal waters of four Gulf Coast states that were impacted by the spill. For over a year, beginning in May 2010, passive sampling devices were used to monitor the bioavailable concentration of PAHs. Prior to shoreline oiling, baseline data were obtained at all the study sites, allowing for direct before and after comparisons of PAH contamination. Significant increases in bioavailable PAHs were seen following the oil spill, however, preoiling levels were observed at all sites by March 2011. A return to elevated PAH concentrations, accompanied by a chemical fingerprint similar to that observed while the site was being impacted by the spill, was observed in Alabama in summer 2011. Chemical forensic modeling demonstrated that elevated PAH concentrations are associated with distinctive chemical profiles.     

Potential for sea otter exposure to remnants of buried oil from the Exxon Valdez oil spill

A study was conducted in 2005 and 2006 to examine the hypothesis that sea otters (Enhydra lutris) continue to be exposed to residues of subsurface oil (SSO) while foraging on shorelines in the northern Knight Island (NKI) area of Prince William Sound, Alaska more than 17 years after the Exxon Valdez oil spill. Forty-three shoreline segments, whose oiling history has been documented by prior surveys, were surveyed. These included all shoreline segments reported by a 2003 NOAA random site survey to contain SSO residues in NKI. Sites were surveyed for the presence and location of otter foraging pits. Only one of 29 SSO sites surveyed was identified as an otter foraging site. Most buried SSO residues are confined to tide elevations above +0.8 m above mean lower low water (MLLW), above the range of intertidal clam habitat. More than 99% of documented intertidal otter pits at all sites surveyed are in the lower intertidal zone (-0.2 to +0.8 m above MLLW), the zone of highest clam abundance. The spatial separation of the otter pits from the locations of SSO residues, both with regard to tidal elevation and lateral separation on the study sites, coupled with the lack of evidence of intertidal otter foraging at SSO sites indicates a low likelihood of exposure of foraging otters to SSO on the shores of the NKI area.     

Differences in phosphorus and nitrogen delivery to the Gulf of Mexico from the Mississippi River Basin

Seasonal hypoxia in the northern Gulf of Mexico has been linked to increased nitrogen fluxes from the Mississippi and Atchafalaya River Basins, though recent evidence shows that phosphorus also influences productivity in the Gulf. We developed a spatially explicit and structurally detailed SPARROW water-quality model that reveals important differences in the sources and transport processes that control nitrogen (N) and phosphorus (P) delivery to the Gulf. Our model simulations indicate that agricultural sources in the watersheds contribute more than 70% of the delivered N and P. However, corn and soybean cultivation is the largest contributor of N (52%), followed by atmospheric deposition sources (16%); whereas P originates primarily from animal manure on pasture and rangelands (37%), followed by corn and soybeans (25%), other crops (18%), and urban sources (12%). The fraction of in-stream P and N load delivered to the Gulf increases with stream size, but reservoir trapping of P causes large local- and regional-scale differences in delivery. Our results indicate the diversity of management approaches required to achieve efficient control of nutrient loads to the Gulf. These include recognition of important differences in the agricultural sources of N and P, the role of atmospheric N, attention to P sources downstream from reservoirs, and better control of both N and P in close proximity to large rivers.     

Identification of the mass spectral signature of organic aerosols from wood burning emissions

Throughout the winter months, the village of Roveredo, Switzerland, frequently experiences strong temperature inversions that contribute to elevated levels of particulate matter. Wood is used as fuel for 75% of the domestic heating installations in Roveredo, which makes it a suitable location to study wood burning emissions in the atmosphere in winter. An Aerodyne quadrupole aerosol mass spectrometer (Q-AMS) was used to characterize the composition of the submicrometer, non-refractory aerosol particles at this location during two field campaigns in March and December 2005. Wood burning was found to be a major source of aerosols at this location in winter. Organics dominated the composition of the aerosols from this source, contributing up to 85% of the total AMS measured mass during the afternoon and evening hours. Carbonaceous particle analysis showed that organic carbon composed up to 86% of the total carbon mass collected at evening times. Results from 14C isotope determination revealed that up to 94% of the organic mass came from non-fossil sources, which can be attributed mostlyto wood burning. The unique combination of off-line 14C isotope analysis and on-line aerosol mass spectrometry was used to identify periods during which organic mass was mainly from wood burning emissions and allowed for the identification of the AMS spectral signature of this source in the atmosphere. The identified ambient signature of wood burning was found to be very similar to the mass spectral signature obtained during the burning of chestnut wood samples in a small stove and also to the spectrum of levoglucosan. Particles from wood burning appeared to be composed of highly oxygenated organic compounds, and mass fragments 60, 73, and 137 have been suggested as marker fragments for wood burning aerosols. Mass fragment 44, which is used as a marker for oxygenated organic aerosols (OOA), contributed about 5% to the total organic signal from primary wood burning sources. The ratio of the organic mass emitted from wood burning to m/z 60 in Roveredo is 36. This ratio may be used to provide an estimate of the organic aerosol mass emitted from wood burning in other locations.     

Storage stability of liver oil from two ray (Rhinoptera bonasus and Aetobatus narinari) species from the Gulf of Mexico

The effect of storage time on the quality of liver oil from two commercial rajiform species (Rhinoptera bonasus and Aetobatus narinari) captured in the Gulf of Mexico (State of Campeche coast line) was evaluated. Oil characterisation was conducted by physical (specific gravity, saponification index and water content) and chemical analyses (fatty acid content, carotenes and tocopherols) whilst storage stability (peroxide value, free fatty acids, conjugated dienes, anisidine value and changes in docosahexaenoic acid, DHA and content) was studied for 87 days at 25 °C. Increases (p < 0.05) in free fatty acids, conjugated dienes, peroxide value and anisidine value, and a decrease (p < 0.05) in DHA were observed during the storage time for both oil species as oxidation proceeded. It was concluded that R. bonasus and A. narinari oils lasted for 52 and 66 days under these storage conditions, respectively.     

Surimi of fish species from the Gulf of Mexico: evaluation of the setting phenomenon

Atlantic croaker (Micropogon undulatus), Mexican flounder (Cyclopsetta chittendeni) and Northern kingfish (Menticirrhus saxatilis) are warm water species abundant in the Gulf of Mexico, usually obtained as shrimp by-catch. Gels from these species were obtained by several treatments: (1) setting at 25°C/3 h followed by cooking at 90°C/15 min; (2) setting at 40°C/30 min and 90°C/15 min; (3) 90°C/15 min (control). Three different additives were studied: 0.66% ammonium chloride, 0.2% EDTA and 0.2% calcium chloride. The setting phenomenon was induced at 40°C in the three species. 0.2% calcium chloride improved shear stress and shear strain in surimi gels from Atlantic croaker and Northern kingfish. 87.98 and 98.49 kPa for shear stress, and 2.23 and 2.15 for shear strain were achieved, respectively.     

Remote sensing study of emissions from motor vehicles in the Metropolitan Area of Mexico City

Remote sensing was employed for the first time to measure nitric oxide (NO) levels of on-road light-duty motor vehicles of the Metropolitan Area of Mexico City (MAMC). The sensor placed at 12 different sites also measured the concentration of CO2, CO, and total hydrocarbons (THC) in the exhaust emissions. A database was compiled containing 122 800 readings, of which 84 650 (69%) records were valid emissions measurements. CO, HC, and NO valid readings were 68.9, 63.4, and 62.9%, respectively, of the total attempted measurements. Furthermore, 42 822 vehicles were number-plate-matched to model year with the information provided by the Inspection/Maintenance Program. The mean emissions of total valid readings for CO, HC, and NO were determined to be 1.31 vol %, 440 ppm (propane), and 914 ppm, respectively. In 1991 and 1994, remote sensing measurements of CO and HC tailpipe emissions were performed in the MAMC in five different locations (30 000 valid readings). Large drops in both pollutants were observed for the intervening years, but sufficient vehicle information was not available at that time to fully explain the observed trends. Compared with those reports, our results point out to a steady decrease in CO and HC exhaust emissions with vehicle model year. The fleet emissions measured exhibit a gamma-distribution, with 10% of the most polluting fleet studied being responsible for 45%, 25%, and 29% of the CO, HC, and NO emissions, respectively. NO emissions in taxis are the highest among the vintage of vehicles, a matter of concern since according to the distance traveled per year, they represent 22% of the total activity in the MAMC.     

Contribution of lubricating oil to particulate matter emissions from light-duty gasoline vehicles in Kansas City

The contribution of lubricating oil to particulate matter (PM) emissions representative of the in-use 2004 light-duty gasoline vehicles fleet is estimated from the Kansas City Light-Duty Vehicle Emissions Study (KCVES). PM emissions are apportioned to lubricating oil and gasoline using aerosol-phase chemical markers measured in PM samples obtained from 99 vehicles tested on the California Unified Driving Cycle. The oil contribution to fleet-weighted PM emission rates is estimated to be 25% of PM emission rates. Oil contributes primarily to the organic fraction of PM, with no detectable contribution to elemental carbon emissions. Vehicles are analyzed according to pre-1991 and 1991-2004 groups due to differences in properties of the fitting species between newer and older vehicles, and to account for the sampling design of the study. Pre-1991 vehicles contribute 13.5% of the KC vehicle population, 70% of oil-derived PM for the entire fleet, and 33% of the fuel-derived PM. The uncertainty of the contributions is calculated from a survey analysis resampling method, with 95% confidence intervals for the oil-derived PM fraction ranging from 13% to 37%. The PM is not completely apportioned to the gasoline and oil due to several contributing factors, including varied chemical composition of PM among vehicles, metal emissions, and PM measurement artifacts. Additional uncertainties include potential sorption of polycyclic aromatic hydrocarbons into the oil, contributions of semivolatile organic compounds from the oil to the PM measurements, and representing the in-use fleet with a limited number of vehicles.     

Polyfluoroalkyl compounds in free-ranging bottlenose dolphins (Tursiops truncatus) from the Gulf of Mexico and the Atlantic Ocean

Polyfluoroalkyl compounds (PFAs) have been used for decades in industrial and commercial products and are now detected worldwide. Concentrations of two major PFA groups, carboxylic acids (PFCAs) and sulfonic acids (PFSAs), were assessed in plasma of bottlenose dolphins from the Gulf of Mexico (Sarasota Bay, FL) and the Atlantic Ocean (Delaware Bay, NJ, Charleston, SC, Indian River Lagoon (IRL), FL, and Bermuda). Eight PFAs were detected in the plasma of all dolphins. Perfluorooctane sulfonate (PFOS) was the predominant compound at all locations (range from 49 ng/g wet weight (w.w.) in dolphins from Bermuda to 1171 ng/g w.w. in plasma of animals from Charleston). Sum of PFA concentrations were significantly higher in animals from Charleston compared to IRL, Sarasota Bay, and Bermuda. Concentrations of several PFAs were negatively associated with age in animals from IRL and Charleston. No differences between gender were observed for all compounds at all locations. An increase in PFA concentrations was associated with a decrease of blubber thickness in animals from Sarasota Bay and IRL. Fluorotelomer 8:2 and 10:2 unsaturated carboxylic acids (FTUCAs), known degradation products of fluorotelomer alcohols and suspected precursors to PFCAs, were detected for the first time at low concentrations in plasma of dolphins.     

Integrated assessment of the spatial variability of ozone impacts from emissions of nitrogen oxides

This paper examines the ozone (O3) damages caused by nitrogen oxides (NO(x)) emissions in different locations around the Atlanta metropolitan area during a summer month. We calculate O3 impacts using a new integrated assessment model that links pollution emissions to their chemical transformation, transport, population exposures, and effects on human health. We find that increased NO(x) emissions in rural areas around Atlanta increase human exposure to ambient O3 twice as much as suburban emissions. However, increased NO(x) emissions in central city Atlanta actually reduce O3 exposures. For downtown emissions, the reduction in human exposures to O3 from titration by NO in the central city outweighs the effects from increased downwind O3. The results indicate that the marginal damage from NO(x) emissions varies greatly across a metropolitan area. The results raise concerns if cap and trade regulations cause emissions to migrate toward higher marginal damage locations.     

Identification of lubrication oil in the particulate matter emissions from engine exhaust of in-service commercial aircraft

Lubrication oil was identified in the organic particulate matter (PM) emissions of engine exhaust plumes from in-service commercial aircraft at Chicago Midway Airport (MDW) and O'Hare International Airport (ORD). This is the first field study focused on aircraft lubrication oil emissions, and all of the observed plumes described in this work were due to near-idle engine operations. The identification was carried out with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF AMS) via a collaborative laboratory and field investigation. A characteristic mass marker of lubrication oil, I(85)/I(71), the ratio of ion fragment intensity between m/z = 85 and 71, was used to distinguish lubrication oil from jet engine combustion products. This AMS marker was based on ion fragmentation patterns measured using electron impact ionization for two brands of widely used lubrication oil in a laboratory study. The AMS measurements of exhaust plumes from commercial aircraft in this airport field study reveal that lubrication oil is commonly present in organic PM emissions that are associated with emitted soot particles, unlike the purely oil droplets observed at the lubrication system vent. The characteristic oil marker, I(85)/I(71), was applied to quantitatively determine the contribution from lubrication oil in measured aircraft plumes, which ranges from 5% to 100%.