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EENV 421 California State University Fullerton Risk Analysis Case Study

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Air quality implications of the Deepwater Horizon oil spill Ann M. Middlebrooka,1, Daniel M. Murphya, Ravan Ahmadova,b, Elliot L. Atlasc, Roya Bahreinia,b, Donald R. Blaked, Jerome Brioudea,b, Joost A. de Gouwa,b, Fred C. Fehsenfelda,b, Gregory J. Frosta,b, John S. Hollowaya,b, Daniel A. Lacka,b, Justin M. Langridgea,b, Rich A. Luebe, Stuart A. McKeena,b, James F. Meaghera, Simone Meinardid, J. Andrew Neumana,b, John B. Nowaka,b, David D. Parrisha, Jeff Peischla,b, Anne E. Perringa,b, Ilana B. Pollacka,b, James M. Robertsa, Thomas B. Ryersona, Joshua P. Schwarza,b, J. Ryan Spackmana,b, Carsten Warnekea,b, and A. R. Ravishankaraa a Chemical Sciences Division, National Oceanic and Atmospheric Administration Earth System Research Laboratory, Boulder, CO 80305; bCooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80309; cRosenstiel School of Marine and Atmospheric Science, University of Miami, Miami, FL 33149; dDepartments of Chemistry and Earth System Science, University of California, Irvine, CA 92697; and e Atmospheric Chemistry Division, National Center for Atmospheric Research, Boulder, CO 80307 Edited by Marcia K. McNutt, US Geological Survey, Reston, VA, and approved October 14, 2011 (received for review June 22, 2011) During the Deepwater Horizon (DWH) oil spill, a wide range of gas and aerosol species were measured from an aircraft around, downwind, and away from the DWH site. Additional hydrocarbon measurements were made from ships in the vicinity. Aerosol particles of respirable sizes were on occasions a significant air quality issue for populated areas along the Gulf Coast. Yields of organic aerosol particles and emission factors for other atmospheric pollutants were derived for the sources from the spill, recovery, and cleanup efforts. Evaporation and subsequent secondary chemistry produced organic particulate matter with a mass yield of 8 4% of the oil mixture reaching the water surface. Approximately 4% by mass of oil burned on the surface was emitted as soot particles. These yields can be used to estimate the effects on air quality for similar events as well as for this spill at other times without these data. Whereas emission of soot from burning surface oil was large during the episodic burns, the mass flux of secondary organic aerosol to the atmosphere was substantially larger overall. We use a regional air quality model to show that some observed enhancements in organic aerosol concentration along the Gulf Coast were likely due to the DWH spill. In the presence of evaporating hydrocarbons from the oil, NOx emissions from the recovery and cleanup operations produced ozone. O n April 20, 2010, an explosion and subsequent leak beneath the Deepwater Horizon (DWH) drilling platform led to the largest marine oil spill in United States history. The air quality issues arising from the oil spill are different for workers at the site than for the population along the coast. Primary emissions are of more concern near the site and secondary pollutants are more important downwind. The key atmospheric pollutants considered in this paper are hydrocarbons (HCs), particulate matter (PM) or aerosol particles, ozone, carbon monoxide, and nitrogen oxides. Four sources of primary air pollutants attributable to the DWH oil spill are detected in our observations: (a) HCs evaporating from the oil; (b) smoke from deliberate burning of the oil slick; (c) combustion products from the flaring of recovered natural gas; and (d) ship emissions from the recovery and cleanup operations. Here, we examine these primary emissions and the subsequent production of ozone and secondary organic aerosol (SOA). Furthermore, we use aircraft data to derive the amount of atmospheric particulate matter formed per mass of oil that reached the surface. These results can be used to estimate implications for air quality during the DWH spill at other times and locations and can also provide information about effects on air quality by past or future spills. cies (Table S1) near the DWH site. HCs were also measured from ships in the vicinity of DWH, including the NOAA R/V Thomas Jefferson that sailed close to the DWH site on June 22–27, 2010. Samples from the ship were taken from about 6–10 m above the water surface. By June 8, a containment cap had been loosely installed on the wellhead and surface recovery vessels were able to capture a fraction of the leaking oil and natural gas. Oil on the sea surface was burned periodically (1, 2) on June 8. On both flights, the aircraft flew a rectangular pattern about 8 km from the DWH site and then flew transects perpendicular to the wind direction at progressively farther distances downwind (Fig. 1). The flights also surveyed the air about 40 km off the Gulf Coast and upwind of DWH. On both days there was a well-mixed marine boundary layer about 600 m deep (3). Most aircraft data were obtained at 200 m altitude with some at lower or higher altitudes to verify the characteristics of the boundary layer and air just above it. Measured concentrations of atmospheric pollutants varied depending on the location of the aircraft or ship relative to the DWH site and the resulting surface oil, the residence time of oil on the surface, chemical reactions of pollutant species in the atmosphere, and meteorological conditions. The mixing ratios of several gaseous and aerosol species at various locations are summarized in Tables S2 and S3. Assuming a constant source of precursors and similar production rates, the factor of 2–3 difference in concentrations between the June 8 and 10 flights is roughly consistent with the variation in the dilution rate due to different wind speeds for the two days. The aircraft transects that were farthest (approximately 47 km) downwind of DWH indicated a plume about 4 km wide (full width half maximum, FWHM) of volatile species such as light alkanes and aromatics that evaporated from the oil (Fig. 2 and Fig. S1). Nitrogen oxides (NOx ¼ NO þ NO2 ), emitted by flaring of recovered natural gas and ship operations close to the spill site, reacted to form nitric acid, peroxyacetyl nitrate (PAN), and other oxidation products that are included with NOx in the total of reactive nitrogen, NOy . The small signal of NOx relative to NOy in this transect indicates that most of the Author contributions: D.M.M., F.C.F., J.F.M., D.D.P., T.B.R., and A.R.R. designed research; A.M.M., D.M.M., R.A., E.L.A., R.B., D.R.B., J.B., J.A.d.G., G.J.F., J.S.H., D.A.L., J.M.L., R.A.L., S.A.M., S.M., J.A.N., J.B.N., J.P., A.E.P., I.B.P., J.M.R., T.B.R., J.P.S., J.R.S., and C.W. performed research; A.M.M., D.M.M., R.A., E.L.A., R.B., D.R.B., J.A.d.G., J.S.H., D.A.L., J.M.L., S.A.M., S.M., J.A.N., J.B.N., J.P., A.E.P., I.B.P., J.M.R., T.B.R., J.P.S., J.R.S., and C.W. analyzed data; and A.M.M., D.M.M., R.A., S.A.M., J.F.M., J.A.N., J.B.N., D.D.P., J.P., J.M.R., T.B.R., C.W., and A.R.R. wrote the paper. Downloaded by guest on January 24, 2022 The authors declare no conflict of interest. Measurements On June 8 and 10, 2010, the National Oceanic and Atmospheric Administration (NOAA) WP-3D aircraft carried an extensive suite of instruments that measured trace gases and aerosol spe20280–20285 ∣ PNAS ∣ December 11, 2012 ∣ vol. 109 ∣ no. 50 This article is a PNAS Direct Submission. 1 To whom correspondence should be addressed. E-mail: Ann.M.Middlebrook@noaa.gov. This article contains supporting information online at www.pnas.org/lookup/suppl/ doi:10.1073/pnas.1110052108/-/DCSupplemental. www.pnas.org/cgi/doi/10.1073/pnas.1110052108 25 -88 -87 -86 -85 29 10 20 Ozone (ppbv) 0 30 Organic Aerosol Mass ( µg m-3 ) Longitude 31 -91 -90 -89 0.6 5 56 0.3 Ozone NOy NOx -87 -86 -85 0.0 3.0 2.5 2.0 54 52 1.5 50 1.0 48 0.5 44 0.0 30 Near Shore Downwind of DWH Site Spill Region 28 Upwind 0 10 20 30 Organic Aerosol Mass ( µg m-3 ) Fig. 1 Track of National Oceanic and Atmospheric Administration WP-3D aircraft flight (markers color-coded by organic aerosol mass concentration) conducted on June 8, 2010 (Upper) and June 10, 2010 (Lower) superimposed on the remotely sensed location of the oil (gray) at the time of the flight. The red star indicates the DWH site. The boxes outlined in black indicate the portions of the flight data that were averaged for Table S2. The wind was light and generally from the northeast on June 8 and steady from the southeast on June 10. Image produced by NOAA/NESDIS Satellite Analysis Branch, based on satellite imagery provided by ESA, CSA, ASI, e-GEOS, infoterra, CSTARS, NASA, and NOAA. NOx was converted to other forms within the roughly 3 h since emission. These narrow plumes were embedded within a plume more than 30 km wide (FWHM) of organic aerosol particles. Results and Discussion HCs Evaporating from Oil That Surfaced. By mass, the largest air emissions from the spill consisted of HCs evaporating from oil. These HCs can affect air quality in three ways. First, some of the measured compounds, including benzene, toluene, and naphthalene, are classified as hazardous air pollutants (http://www.epa.
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