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  • 1
    Publication Date: 2022-05-25
    Description: Author Posting. © IOP Publishing, 2012. This article is posted here by permission of IOP Publishing. Re-use is limited to non-commercial purposes. The definitive version was published in Environmental Research Letters 7 (2012): 015301, doi:10.1088/1748-9326/7/1/015301.
    Description: The discovery of oiled and non-oiled honeycomb material in the Gulf of Mexico surface waters and along coastal beaches shortly after the explosion of Deepwater Horizon sparked debate about its origin and the oil covering it. We show that the unknown pieces of oiled and non-oiled honeycomb material collected in the Gulf of Mexico were pieces of the riser pipe buoyancy module of Deepwater Horizon. Biomarker ratios confirmed that the oil had originated from the Macondo oil well and had undergone significant weathering. Using the National Oceanic and Atmospheric Administration's records of the oil spill trajectory at the sea surface, we show that the honeycomb material preceded the front edge of the uncertainty of the oil slick trajectory by several kilometers. We conclude that the observation of debris fields deriving from damaged marine materials may be incorporated into emergency response efforts and forecasting of coastal impacts during future offshore oil spills, and ground truthing predicative models.
    Description: This research was supported by NSF grant OCE-1043976 to CR.
    Keywords: Deepwater Horizon ; Macondo well ; Gulf of Mexico ; Oil spill ; Floating debris
    Repository Name: Woods Hole Open Access Server
    Type: Article
    Format: application/pdf
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  • 2
    Publication Date: 2022-05-26
    Description: © American Chemical Society, 2016. This article is distributed under the terms of the AuthorsChoice License. The definitive version was published in Environmental Science & Technology 50 (2016): 7397–7408, doi:10.1021/acs.est.5b04617.
    Description: With the expansion of offshore petroleum extraction, validated models are needed to simulate the behaviors of petroleum compounds released in deep (〉100 m) waters. We present a thermodynamic model of the densities, viscosities, and gas–liquid−water partitioning of petroleum mixtures with varying pressure, temperature, and composition based on the Peng–Robinson equation-of-state and the modified Henry’s law (Krychevsky−Kasarnovsky equation). The model is applied to Macondo reservoir fluid released during the Deepwater Horizon disaster, represented with 279–280 pseudocomponents, including 131–132 individual compounds. We define 〉n-C8 pseudocomponents based on comprehensive two-dimensional gas chromatography (GC × GC) measurements, which enable the modeling of aqueous partitioning for n-C8 to n-C26 fractions not quantified individually. Thermodynamic model predictions are tested against available laboratory data on petroleum liquid densities, gas/liquid volume fractions, and liquid viscosities. We find that the emitted petroleum mixture was ∼29–44% gas and ∼56–71% liquid, after cooling to local conditions near the broken Macondo riser stub (∼153 atm and 4.3 °C). High pressure conditions dramatically favor the aqueous dissolution of C1−C4 hydrocarbons and also influence the buoyancies of bubbles and droplets. Additionally, the simulated densities of emitted petroleum fluids affect previous estimates of the volumetric flow rate of dead oil from the emission source.
    Description: This research was made possible by grants from the NSF (OCE- 0960841, OCE-1043976, and EAR-0950600) and the Gulf of Mexico Research Initiative (GoMRI) to the C-IMAGE and DEEP-C consortia.
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 3
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    ACS (American Chemical Society)
    In:  Environmental Science & Technology, 51 (5). pp. 3001-3011.
    Publication Date: 2020-11-25
    Description: The chemical parameters needed to explain and predict bioavailability, biodynamics, and baseline toxicity are not readily available for most nonpolar chemicals detected in the environment. Here, we demonstrate that comprehensive two-dimensional gas chromatography (GC × GC) retention times can be used to predict 26 relevant properties for nonpolar chemicals, specifically: partition coefficients for diverse biotic media and passive sampler phases; aquatic baseline toxicity; and relevant diffusion coefficients. The considered biotic and passive sampler phases include membrane and storage lipids, serum and muscle proteins, carbohydrates, algae, mussels, polydimethylsiloxane, polyethylene, polyoxymethylene, polyacrylate, polyurethane, and semipermeable membrane devices. GC × GC-based chemical property predictions are validated with a compilation of 1038 experimental property data collected from the literature. As an example application, we overlay a map of baseline toxicity to fathead minnows onto the separated analyte signal of a polychlorinated alkanes (chlorinated paraffins) technical mixture that contains 7820 congeners. In a second application, GC × GC-estimated properties are used to parametrize multiphase partitioning models for mammalian tissues and organs. In a third example, we estimate chemical depuration kinetics for mussels. Finally, we illustrate an approach to screen the GC × GC chromatogram for nonpolar chemicals of potentially high concern, defined based on their GC × GC-estimated biopartitioning properties, diffusion properties, and baseline toxicity.
    Type: Article , PeerReviewed
    Format: text
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  • 4
    Publication Date: 2023-02-08
    Description: Explaining the dynamics of gas-saturated live petroleum in deep water remains a challenge. Recently, Pesch et al. (Environ. Eng. Sci. 2018, 35, 289−299) reported laboratory experiments on methane-saturated oil droplets under emulated deep-water conditions, providing an opportunity to elucidate the underlying dynamical processes. We explain these observations with the Texas A&M Oil spill/Outfall Calculator (TAMOC), which models the pressure-, temperature-, and composition-dependent interactions between: oil-gas phase transfer; aqueous dissolution; and densities and volumes of liquid oil droplets, gas bubbles, and two-phase droplet-bubble pairs. TAMOC reveals that aqueous dissolution removed 〉95% of the methane from ~3.5-mm live oil droplets within 14.5 min, prior to gas bubble formation, during the experiments of Pesch et al. Additional simulations indicate that aqueous dissolution, fluid density changes, and gas-oil phase transitions (ebullition, condensation) may all contribute to the fates of live oil and gas in deep water, depending on the release conditions. Illustrative model scenarios suggest that 5-mm diameter gas bubbles released at 〈470 m water depth can transport methane, ethane, and propane to the water surface. Ethane and propane can reach the water surface from much deeper releases of 5-mm diameter live oil droplets, during which ebullition occurs at water depths of 〈70 m.
    Type: Article , PeerReviewed
    Format: text
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  • 5
    Publication Date: 2024-02-07
    Description: Petroleum substances, as archetypical UVCBs (substances of unknown or variable composition, complex reaction products, or biological substances), pose a challenge for chemical risk assessment as they contain hundreds to thousands of individual constituents. It is particularly challenging to determine the biodegradability of petroleum substances since each constituent behaves differently. Testing the whole substance provides an average biodegradation, but it would be effectively impossible to obtain all constituents and test them individually. To overcome this challenge, comprehensive two-dimensional gas chromatography (GC × GC) in combination with advanced data-handling algorithms was applied to track and calculate degradation half-times (DT50s) of individual constituents in two dispersed middle distillate gas oils in seawater. By tracking 〉1000 peaks (representing ∼53–54% of the total mass across the entire chromatographic area), known biodegradation patterns of oil constituents were confirmed and extended to include many hundreds not currently investigated by traditional one-dimensional GC methods. Approximately 95% of the total tracked peak mass biodegraded after 64 days. By tracking the microbial community evolution, a correlation between the presence of functional microbial communities and the observed progression of DT50s between chemical classes was demonstrated. This approach could be used to screen the persistence of GC × GC-amenable constituents of petroleum substance UVCBs.
    Type: Article , PeerReviewed
    Format: text
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