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Sampling of the smoke plumes from the BP Deepwater Horizon surface oil burns led to the unintentional collection of soot particles on the sail of an instrument-bearing, tethered aerostat. This first-ever plume sampling from oil burned at an actual spill provided an opportunistic sample from which to characterize the particles' chemical properties for polycyclic aromatic hydrocarbons (PAHs), organic carbon, elemental carbon, metals, and polychlorinated dibenzodioxins/dibenzofurans (PCDDs/PCDFs) and physical properties for size and nanostructure. Thermal-optical analyses indicated that the particulate matter was 93% carbon with 82% being refractory elemental carbon. PAHs accounted for roughly 68 mu/g of the PM filter mass and 5 mg/kg oil burned, much lower than earlier laboratory based studies. Microscopy indicated that the soot is distinct from more common soot by its aggregate size, primary particle size, and nanostructure. PM-bound metals were largely unremarkable but PCDD/PCDF formation was observed, contrary to other's findings. Levels of lighter PCDD/PCDF and PAH compounds were reduced compared to historical samples, possibly due to volatilization or photo-oxidation. Published by Elsevier Ltd.