Quantitative information regarding the endmember composition of the gas and oil that flowed from the Macondo well during the Deepwater Horizon oil spill is essential for determining the oil flow rate, total oil volume released, and trajectories and fates of hydrocarbon components in the marine environment. Using isobaric gas-tight samplers, we collected discrete samples directly above the Macondo well on June 21, 2010, and analyzed the gas and oil. We found that the fluids flowing from the Macondo well had a gas-to-oil ratio of 1,600 standard cubic feet per petroleum barrel. Based on the measured endmember gas-to-oil ratio and the Federally estimated net liquid oil release of 4.1 million barrels, the total amount of C 1 -C 5 hydrocarbons released to the water column was 1.7 × 10 11 g. The endmember gas and oil compositions then enabled us to study the fractionation of petroleum hydrocarbons in discrete water samples collected in June 2010 within a southwest trending hydrocarbon-enriched plume of neutrally buoyant water at a water depth of 1,100 m. The most abundant petroleum hydrocarbons larger than C 1 -C 5 were benzene, toluene, ethylbenzene, and total xylenes at concentrations up to 78 μg L −1 . Comparison of the endmember gas and oil composition with the composition of water column samples showed that the plume was preferentially enriched with water-soluble components, indicating that aqueous dissolution played a major role in plume formation, whereas the fates of relatively insoluble petroleum components were initially controlled by other processes.Gulf of Mexico | subsurface plumes D uring the 3 mo following April 20, 2010, the Macondo well emitted several million barrels of gas and oil at the seafloor of the Gulf of Mexico following the sinking of the Deepwater Horizon drilling platform. Relative to oil spills occurring at the sea surface, petroleum hydrocarbons experienced a unique set of processes following their release at 1.5-km depth (1-4). This spill demonstrates the importance of interwoven chemical, physical, and biological processes in regulating the transport and fate of hydrocarbons in the deep marine environment. Compositional information for petroleum (gas and oil) released by the well at the seafloor is essential for evaluating the fates of hydrocarbons in the sea. Moreover, such information provides direct constraints on estimates of the total mass of individual hydrocarbons released to the environment and the flow rates at the site of the spill (5). Gases are of particular interest because the gas fraction represents a large component of the carbon released, and it was biodegraded rapidly in the water column (3, 4). Compositional data for released oil is also necessary for forensic analyses when distinguishing Macondo well oil from hydrocarbons released from other sources in the Gulf of Mexico.Numerous studies have examined factors that influence the compositional evolution of oil spilled at the sea surface (6-10), where evaporation and dissolution may simultaneously remove hydrocarbons fr...

Recently, asphaltenes have been shown to form nanoaggregates in toluene at very low concentrations (10 -4 mass fraction). Subsequently, in situ analysis of a 3000 ft vertical column of crude oil by downhole fluid analysis (DFA) indicated that the asphaltenes in a black crude oil exhibit gravitational sedimentation according to the Boltzmann distribution and that the asphaltene colloidal size is ∼2 nm. Here, we perform a follow-up study of a reservoir black oil from a different field. The black oil in a 658 ft vertical column is analyzed by DFA and advanced laboratory analytical chemical methods. An asphaltene colloidal particle size is found to be ∼2 nm according to the Archimedes buoyancy term in the Boltzmann distribution. In addition, an equation of state (EoS) approach based on literature critical constants and molecular weights for asphaltenes gives an aggregation number of ∼8. Molecular compositional similarities between different oil samples were established with comprehensive two-dimensional gas chromatography (GC × GC). Likewise, results from electrospray ionization Fourier transform ion cyclotron resonance mass spectroscopy (ESI FT-ICR MS) of the samples are consistent with the oils being from the same equilibrium column of oil. The results herein support a growing body of literature indicating that asphaltenes in black oils form relatively tightly bonded nanoaggregates of a single size range. The similarity of results between asphaltenes in crude oil and asphaltenes in toluene points to a very limited role of resins in these nanoaggregates, in contrast to much speculation. The implications of this work on the determination of reservoir connectivity are discussed.