1. Characterization of the Particulate Emissions from the BP Deepwater Horizon Spill Surface Oil Burns Brian Gullett Dennis Tabor Michael Hays U.S. Environmental Protection Agency, Office of Research and Development (E343-04), Research Triangle Park, NC 27711, U.S.A. Gullett.brian@epa.gov 6/13/20161 U.S. Environmental Protection Agency

2. In situ oil burns Procedure Two vessels collect oil by using a fireproof collection boom. An “igniter” boat places a starter charge (gelled diesel in a plastic container with foam flotation and a road flare) within the boom’s oil pool to promote ignition. The burning time can vary from minutes to hours. Collection of oil Ignition of the oil In situ oil burn Reduces spilled oil at sea. Minimizes contamination of coastal marine environments. Oil

3. Sampling emissions at the Gulf in situ oil burns EPA/ORD developed an aerostat- lofted sampler, termed the “Flyer” The Flyer was positioned into the plume for sampling emissions during the 2010 in situ burns The “Flyer” In situ burns of collected oil

4. Aerostat-lofted sampling instruments 4 meter-diameter (13 feet), helium-filled aerostat. The aerostat was launched from the deck of a 67 m (220 ft) long oil platform work boat The aerostat was: tethered to an electrically powered winch using one 600 m (2,000 ft) long Spectra line. maneuvered horizontally by moving the boat. 67 m (220 ft) long oil platform work boat. Spectra lineElectrically powered winch

5. Sampling for PCDD/PCDF at the Gulf in situ oil burns ORD Assistant Administrator Paul Anastas requested PCDD/PCDF measurements of in situ burn plumes Insufficient precedent measurements had been taken There was across-Agency participation in discussion leading up to the sampling effort MOVIE HERE FROM THE GULF FIRES

6. Sampling and analytical methods for the plume sample* Target compoundSampling methodSampling Flow rateAnalytical method PCDD/PCDFPUFP/XAD/PUFP/Filter EPA Method TO-9A 160 L/minGC/HRMS Total PM47 mm Filter13 L/minAnalytical balance CO 2 LiCOR CEM EPA Method 3A Readings every second NDIR cell The carbon mass balance method was used to calculate emission factors. We assumed: that > 95% of the elemental carbon from the material burned is emitted to the atmosphere as CO 2 or Particulate Matter-bound carbon. complete mixing of the plume, i.e. the pollutants and the carbon emitted are assumed to be proportionally distributed throughout the plume. *Aurell, J. and Gullett, B. “Aerostat Sampling of PCDD/PCDF Emission from the Gulf Oil Spill In Situ Burns, Environ. Sci. Technol., 44, 9431-9437, 2010.

7. Sampling summary July 13 - July 16, 2010 4 days, 27 plumes. Average plume sampling 8 min, when the CO 2 concentration exceeded the 400 ppm trigger setting. 28 min longest plume sampling. 215 min of total plume sampling. 1,448 min of total background sampling. Average CO 2 over ambient +70 ppm. 1.32 g carbon from CO 2. 0.090 g carbon from PM. 1.4 g of total carbon sampled. One single composite PCCD/F plume sample. 5 PM samples. 2.18 g of sail-captured solids

8. The “Skirt Sample” 6/13/2016U.S. Environmental Protection Agency8 A large amount of plume solids were caught in the skirt which were collected for subsequent analyses. This sample is the subject of this presentation. The PM concentration was 8.8% of the oil carbon burned.

9. Metal Results 6/13/2016U.S. Environmental Protection Agency9 ElementResult (ppm)g metal/kg CNOBE'93 Lithium50.00 Boron990.01X SodiumMAJORX MagnesiumMAJORX Aluminum79680.70X Phosphorus1580.01 Potassium24920.22 CalciumMAJOR Titanium2540.02X Manganese970.01X Iron46670.41X Cobalt30.00 Nickel490.00 Copper150.00 Zinc820.01X Gallium20.00 Rubidium80.00 Strontium2650.02 Yttrium80.00 Zirconium60.00 Barium3030.03X Lanthanum60.00 Cerium120.00 Neodymium60.00 Lead1040.01 X = metals found in significant quantities from New Foundland offshore burn experiments, NOBE ‘93

10. PCDD/PCDF Results 6/13/2016U.S. Environmental Protection Agency10 PCDD/PCDF congener fractions, mass of congener/total mass of TEF-weighted PCDD or PCDF congeners (ND =0) Similar congener profiles suggest that the skirt sample is representative of the 2010 gas + solid plume sample for semi-volatiles and provide support for the limited 2010 sample results.

11. PCDD/PCDF Results 6/13/2016U.S. Environmental Protection Agency11 Aurell, J. and Gullett, B. “Aerostat Sampling of PCDD/PCDF Emission from the Gulf Oil Spill In Situ Burns, Environ. Sci. Technol., 44, 9431-9437, 2010. Similar emission factors for the skirt and plume samples support the methodology and results from the Gulf 2010 study.

12. Organic constituents on particles 6/13/2016U.S. Environmental Protection Agency12 Two samples Solvent-extracted filter punch Toluene extract from 2010 sample GC/MS triple quadrapole in full scan mode Thermal-Optical analysis

13. PM organic results Carbonaceous (93%), high EC (81.6%), OC (18.4%) 64 µg/g of PAHs in the toluene extract (low) Copious PAHs in filter extract, including coronene Oil markers, such as hopanes and steranes, in high concentrations; would allow distant plume tracing 6/13/2016U.S. Environmental Protection Agency13

14. Conclusions Poor combustion quality Very high PM emission factor ~ 9% High EC Relatively low PCDD/PCDF emission factor –On the order of wood burning –approximately 0.01% of the annual U.S. inventory of quantified sources. Metals comparable to past results Additional pollutant characterization of plumes would enable a more comprehensive analysis of the environmental costs and benefits of in situ oil burning 6/13/2016U.S. Environmental Protection Agency14

15. Thank you! Special thanks to Dr. Johanna Aurell (Univ Dayton);Rob Gribble (ISSI, Inc.); Chris Pressley, Bob Wright, Shawn Ryan, Jeff Frithsen, Cindy Sonich-Mullin (U.S. EPA); and MSTCS Andrew Jaeger (USCG).

16. Characterization of the Particulate Emissions from the BP Deepwater Horizon Spill Surface Oil Burns Brian Gullett Dennis Tabor Michael Hays U.S. Environmental Protection Agency, Office of Research and Development (E343-04), Research Triangle Park, NC 27711, U.S.A. Gullett.brian@epa.gov 6/13/201616 U.S. Environmental Protection Agency