Investigating the fate of petroleum fluids released in the marine environment with comprehensive two-dimensional gas chromatography and transport models

Anthropogenic releases of petroleum fluids, which contain thousands of compounds, represent a threat to marine environments. However, there was a lack of models able to explain the independent behaviors of the numerous compounds of a spilled petroleum fluid, in particular for a release in deep waters that is subjected to elevated pressures. In this thesis, we present new models to predict the behavior of hundreds of petroleum compounds upon release in the environment, both at the sea surface and in deep waters. We also propose advances to data-analysis techniques. Comprehensive two-dimensional gas chromatography (GC×GC) is used for quantitative and detailed analysis of petroleum composition, enabling the development of models able to predict the independent behavior of numerous petroleum compounds. Nevertheless, uncontrolled run-to-run variations of analyte retention times are encountered in GC×GC chromatograms and this hampers quantitative comparisons. Therefore a new alignment algorithm was developed, enabling improved analysis in subsequent chapters. During the early period after release at sea surface (first hours), several petroleum hydrocarbons fractionate into air and water. However there is a lack of detailed compositional data for this early period, which cannot usually be sampled. We developed a model of evaporation and aqueous dissolution applicable to a whole GC×GC chromatogram and to individual compounds. This model was validated using data recorded previously during a 4.3 m3 oil release experiment conducted on the North Sea. Our model enabled us to investigate the fractionation of hydrocarbons during this early period, and to estimate the expected outcome when several environmental conditions are varied. The thermodynamic properties of petroleum gas and liquid phases released in deep waters are poorly known. To address this need, we present a thermodynamic model of the gas-liquid-water partitioning, densities, and viscosities of petroleum mixtures with varying composition, as a function of pressure, temperature, and water salinity. This enabled us to provide estimates for poorly characterized properties at ambient conditions encountered at emission depth during the 2010 Deepwater Horizon disaster, and to investigate the effect of depth on equilibrium aqueous solubility. The hydrocarbon fractionation reported during the Deepwater Horizon disaster had not been mechanistically explained. To address this need, we developed a model of the combined effects of buoyant plume dynamics and aqueous dissolution kinetics, including relevant deep-water effects. This is the first study to demonstrate mechanistically that aqueous dissolution was a major process, with ~27% of the emitted mass dissolved during ascent. Our model predictions also provide insight in the debate on whether the injection of dispersant at the emission source led to the formation of <300 ¿m droplets that stayed submerged for weeks or months. Biodegradation plays a major role in the natural attenuation of oil spills. However, limited information is available about biodegradation of different saturated hydrocarbon classes, despite that oils are composed mostly of saturates. In collaboration with the Woods Hole Oceanographic Institution, we studied weathered oil samples collected on Gulf of Mexico beaches 12¿19 months after the Deepwater Horizon disaster. We determined the difference in susceptibility to biodegradation for different saturates in the n-C22¿n-C29 rang

Integral models for bubble, droplet, and multiphase plume dynamics in stratification and crossflow

We present the development and validation of a numerical modeling suite for bubble and droplet dynamics of multiphase plumes in the environment. This modeling suite includes real-fluid equations of state, Lagrangian particle tracking, and two different integral plume models: an Eulerian model for a double-plume integral model in quiescent stratification and a Lagrangian integral model for multiphase plumes in stratified crossflows. Here, we report a particle tracking algorithm for dispersed-phase particles within the Lagrangian integral plume model and a comprehensive validation of the Lagrangian plume model for single- and multiphase buoyant jets. The model utilizes literature values for all entrainment and spreading coefficients and has one remaining calibration parameter (Formula presented.), which reduces the buoyant force of dispersed phase particles as they approach the edge of a Lagrangian plume element, eventually separating from the plume as it bends over in a crossflow. We report the calibrated form (Formula presented.), where b is the plume half-width, and r is the distance of a particle from the plume centerline. We apply the validated modeling suite to simulate two test cases of a subsea oil well blowout in a stratification-dominated crossflow. These tests confirm that errors from overlapping plume elements in the Lagrangian integral model during intrusion formation for a weak crossflow are negligible for predicting intrusion depth and the fate of oil droplets in the plume. The Lagrangian integral model has the added advantages of being able to account for entrainment from an arbitrary crossflow, predict the intrusion of small gas bubbles and oil droplets when appropriate, and track the pathways of individual bubbles and droplets after they separate from the main plume or intrusion layer

Simulating and Quantifying Multiple Natural Subsea CO2 Seeps at Panarea Island (Aeolian Islands, Italy) as a Proxy for Potential Leakage from Subseabed Carbon Storage Sites

Carbon dioxide (CO2) capture and storage (CCS) has been discussed as a potentially significant mitigation option for the ongoing climate warming. Natural CO2 release sites serve as natural laboratories to study subsea CO2 leakage in order to identify suitable analytical methods and numerical models to develop best-practice procedures for the monitoring of subseabed storage sites. We present a new model of bubble (plume) dynamics, advection-dispersion of dissolved CO2, and carbonate chemistry. The focus is on a medium-sized CO2 release from 294 identified small point sources around Panarea Island (South-East Tyrrhenian Sea, Aeolian Islands, Italy) in water depths of about 40–50 m. This study evaluates how multiple CO2 seep sites generate a temporally variable plume of dissolved CO2. The model also allows the overall flow rate of CO2 to be estimated based on field measurements of pH. Simulations indicate a release of ∼6900 t y–1 of CO2 for the investigated area and highlight an important role of seeps located at >20 m water depth in the carbon budget of the Panarea offshore gas release system. This new transport-reaction model provides a framework for understanding potential future leaks from CO2 storage sites

Dynamics of live oil droplets and natural gas bubbles in deep water

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

Utility of natural and artificial geochemical tracers for leakage monitoring and quantification during an offshore controlled CO2 release experiment

To inform cost-effective monitoring of offshore geological storage of carbon dioxide (CO2), a unique field experiment, designed to simulate leakage of CO2 from a sub-seafloor storage reservoir, was carried out in the central North Sea. A total of 675 kg of CO2 were released into the shallow sediments (∼3 m below seafloor) for 11 days at flow rates between 6 and 143 kg d-1. A set of natural, inherent tracers (13C, 18O) of injected CO2 and added, non-toxic tracer gases (octafluoropropane, sulfur hexafluoride, krypton, methane) were used to test their applicability for CO2 leakage attribution and quantification in the marine environment. All tracers except 18O were capable of attributing the CO2 source. Tracer analyses indicate that CO2 dissolution in sediment pore waters ranged from 35 % at the lowest injection rate to 41% at the highest injection rate. Direct measurements of gas released from the sediment into the water column suggest that 22 % to 48 % of the injected CO2 exited the seafloor at, respectively, the lowest and the highest injection rate. The remainder of injected CO2 accumulated in gas pockets in the sediment. The methodologies can be used to rapidly confirm the source of leaking CO2 once seabed samples are retrieved

Quantification of dissolved CO2 plumes at the Goldeneye CO2-release experiment

According to many prognostic scenarios by the Intergovernmental Panel on Climate Change (IPCC), a scaling-up of carbon dioxide (CO2) capture and storage (CCS) by several orders-of-magnitude is necessary to meet the target of ≤2 °C global warming by 2100 relative to preindustrial levels. Since a large fraction of the predicted CO2 storage capacity lies offshore, there is a pressing need to develop field-tested methods to detect and quantify potential leaks in the marine environment. Here, we combine field measurements with numerical models to determine the flow rate of a controlled release of CO2 in a shallow marine setting at about 119 m water depth in the North Sea. In this experiment, CO2 was injected into the sediment at 3 m depth at 143 kg d-1. The new leakage monitoring tool predicts that 91 kg d-1 of CO2 escaped across the seafloor, and that 51 kg d-1 of CO2 were retained in the sediment, in agreement with independent field estimates. The new approach relies mostly on field data collected from ship-deployed technology (towed sensors, Acoustic Doppler current profiler—ADCP), which makes it a promising tool to monitor existing and upcoming offshore CO2 storage sites and to detect and quantify potential CO2 leakage

Ensuring efficient and robust offshore storage – The role of marine system modelling

This paper describes the utility of developing marine system models to aid the efficient and regulatory compliant development of offshore carbon storage, maximising containment assurance by well-planned monitoring strategies. Using examples from several model systems, we show that marine models allow us to characterize the chemical perturbations arising from hypothetical release scenarios whilst concurrently quantifying the natural variability of the system with respect to the same chemical signatures. Consequently models can identify a range of potential leakage anomaly detection criteria, identifying the most sensitive discriminators applicable to a given site or season. Further, using models as in-silico testbeds we can devise the most cost-efficient deployment of sensors to maximise detection of CO2 leakage. Modelling studies can also contribute to the required risk assessments, by quantifying potential impact from hypothetical release scenarios. Finally, given this demonstrable potential we discuss the challenges to ensuring model systems are available, fit for purpose and transferable to CCS operations across the globe

Aberrant in Vivo T Helper Type 2 Cell Response and Impaired Eosinophil Recruitment in Cc Chemokine Receptor 8 Knockout Mice

Chemokine receptors transduce signals important for the function and trafficking of leukocytes. Recently, it has been shown that CC chemokine receptor (CCR)8 is selectively expressed by Th2 subsets, but its functional relevance is unclear. To address the biological role of CCR8, we generated CCR8 deficient (−/−) mice. Here we report defective T helper type 2 (Th2) immune responses in vivo in CCR8−/− mice in models of Schistosoma mansoni soluble egg antigen (SEA)-induced granuloma formation as well as ovalbumin (OVA)- and cockroach antigen (CRA)-induced allergic airway inflammation. In these mice, the response to SEA, OVA, and CRA showed impaired Th2 cytokine production that was associated with aberrant type 2 inflammation displaying a 50 to 80% reduction in eosinophils. In contrast, a prototypical Th1 immune response, elicited by Mycobacteria bovis purified protein derivative (PPD) was unaffected by CCR8 deficiency. Mechanistic analyses indicated that Th2 cells developed normally and that the reduction in eosinophil recruitment was likely due to systemic reduction in interleukin 5. These results indicate an important role for CCR8 in Th2 functional responses in vivo