Comprehensive Two-Dimensional Gas Chromatography with Peak Tracking for Screening of Constituent Biodegradation in Petroleum UVCB Substances.

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.

Autonomous Large-Scale Radon Mapping and Buoyant Plume Modeling Quantify Deep Submarine Groundwater Discharge: A Novel Approach Based on a Self-Sufficient Open Ocean Vehicle.

Groundwater discharge into the sea occurs along many coastlines around the world in different geological settings and constitutes an important component of global water and matter budget. Estimates of how much water flows into the sea worldwide vary widely and are largely based on onshore studies and hydrological or hydrogeological modeling. In this study, we propose an approach to quantify a deep submarine groundwater outflow from the seafloor by using autonomously measured ocean surface data, i.e., 222Rn as groundwater tracer, in combination with numerical modeling of plume transport. The model and field data suggest that groundwater outflows from a water depth of ∼100 m can reach the sea surface implying that several cubic meters per second of freshwater are discharged into the sea. We postulate an extreme rainfall event 6 months earlier as the likely trigger for the groundwater discharge. This study shows that measurements at the sea surface, which are much easier to conduct than discharge measurements at the seafloor, can be used not only to localize submarine groundwater discharges but, in combination with plume modeling, also to estimate the magnitude of the release flow rate.

Relative sensitivity of hydrodynamic, thermodynamic, and chemical processes for simulating the buoyant multiphase plume and surfacing flows of an oil and gas blowout.

Deepwater hydrocarbon releases experience complex chemical and physical processes. To assess simplifications of these processes on model predictions, we present a sensitivity analysis using simulations for the Deepwater Horizon oil spill. We compare the buoyant multiphase plume metrics (trap height, rise time etc), the hydrocarbon mass flowrates at the near-field plume termination and their mass fractions dissolved in the water column and reaching the water surface. The baseline simulation utilizes a 19-component hydrocarbon model, live-fluid state equations, hydrate dynamics, and heat and mass transfer. Other simulations turn-off each of these processes, with the simplest one using inert oil and methane gas. Plume metrics are the least sensitive to the modeled processes and can be matched by adjusting the release buoyancy flux. The mass flowrate metrics are more sensitive. Both liquid- and gas-phase mass transfer should be modeled for accurate tracking of soluble components (e.g. C1 - C7 hydrocarbons) in the environment.

An evaluation of models that estimate droplet size from subsurface oil releases.

Droplet size substantially affects the fate of oil released from deep subsea leaks. A baseline dataset of volume-median droplet diameters (d50), culled from ~250 laboratory observations, is used to validate seven droplet-size models. Four models compare reasonably well, having 95% confidence limits in d50 of ~±50%. Simulations with a near-field fate model (TAMOC) reveals that the four best-performing models, with d50 of 1.3-2.2 mm, agree similarly with observed fractionation of petroleum compounds in the water column during June 4-July 15, 2010. Model results suggest that, had a higher dose of dispersant been applied at the wellhead during Deepwater Horizon oil spill (DWH), the d50 would have dropped by an order of magnitude, reducing surfacing C1-C9 volatiles by 3.5×. Model uncertainty is found to be substantial for DWH-like blowouts treated with chemical dispersants, suggesting the need for further droplet-size model improvement.

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 (4), 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 a <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.

The treatment of biodegradation in models of sub-surface oil spills: A review and sensitivity study.

Biodegradation is important for the fate of oil spilled in marine environments, yet parameterization of biodegradation varies across oil spill models, which usually apply constant first-order decay rates to multiple pseudo-components describing an oil. To understand the influence of model parameterization on the fate of subsurface oil droplets, we reviewed existing algorithms and rates and conducted a model sensitivity study. Droplets were simulated from a blowout at 2000 m depth and were either treated with sub-surface dispersant injection (2% dispersant to oil ratio) or untreated. The most important factor affecting oil fate was the size of the droplets, with biodegradation contributing substantially to the fate of droplets ≤0.5 mm. Oil types, which were similar, had limited influence on simulated oil fate. Model results suggest that knowledge of droplet sizes and improved estimation of pseudo-component biodegradation rates and lag times would enhance prediction of the fate and transport of subsurface oil.

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.

Oil spill modeling in deep waters: Estimation of pseudo-component properties for cubic equations of state from distillation data.

Deep-water oil spills represent a major, localized threat to marine ecosystems. Multi-purpose computer models have been developed to predict the fate of spilled oil. These models include databases of pseudo-components from distillation cut analysis for hundreds of oils, and have been used for guiding response action, damage assessment, and contingency planning for marine oil spills. However, these models are unable to simulate the details of deep-water, high-pressure chemistry. We present a new procedure to calculate the chemical properties necessary for such simulations that we validate with 614 oils from the ADIOS oil library. The calculated properties agree within 20.4% with average values obtained from data for measured compounds, for 90% of the chemical properties. This enables equation-of-state calculations of dead oil density, viscosity, and interfacial tension. This procedure enables development of comprehensive oil spill models to predict the behavior of petroleum fluids in the deep sea.

Petroleum dynamics in the sea and influence of subsea dispersant injection during Deepwater Horizon.

During the Deepwater Horizon disaster, a substantial fraction of the 600,000-900,000 tons of released petroleum liquid and natural gas became entrapped below the sea surface, but the quantity entrapped and the sequestration mechanisms have remained unclear. We modeled the buoyant jet of petroleum liquid droplets, gas bubbles, and entrained seawater, using 279 simulated chemical components, for a representative day (June 8, 2010) of the period after the sunken platform's riser pipe was pared at the wellhead (June 4-July 15). The model predicts that 27% of the released mass of petroleum fluids dissolved into the sea during ascent from the pared wellhead (1,505 m depth) to the sea surface, thereby matching observed volatile organic compound (VOC) emissions to the atmosphere. Based on combined results from model simulation and water column measurements, 24% of released petroleum fluid mass became channeled into a stable deep-water intrusion at 900- to 1,300-m depth, as aqueously dissolved compounds (∼23%) and suspended petroleum liquid microdroplets (∼0.8%). Dispersant injection at the wellhead decreased the median initial diameters of simulated petroleum liquid droplets and gas bubbles by 3.2-fold and 3.4-fold, respectively, which increased dissolution of ascending petroleum fluids by 25%. Faster dissolution increased the simulated flows of water-soluble compounds into biologically sparse deep water by 55%, while decreasing the flows of several harmful compounds into biologically rich surface water. Dispersant injection also decreased the simulated emissions of VOCs to the atmosphere by 28%, including a 2,000-fold decrease in emissions of benzene, which lowered health risks for response workers.

Pixel-by-pixel correction of retention time shifts in chromatograms from comprehensive two-dimensional gas chromatography coupled to high resolution time-of-flight mass spectrometry.

A pixel-by-pixel method for correcting retention time (RT) shifts in whole chromatograms from comprehensive two-dimensional gas chromatography coupled to high-resolution time-of-flight mass spectrometry (GC×GC-HRTOFMS) is introduced. A previously developed robust algorithm for correcting RT shifts was extended to high-resolution mass-spectral data. The performance of the new method in terms of decreasing RT shifts and peak volume changes was tested on GC×GC-HRTOFMS data. The RT shift correction algorithm, using linear interpolation for the 1st dimension and Sibson natural neighbor interpolation for the 2nd dimension, performed well for systematically shifted data acquired using two different temperature programs in terms of decreasing RT differences and alterations to the peak volumes and mass spectra. A modified RT shift correction algorithm, using Sibson natural neighbor for both dimensions, performed better for RT shifts caused by column damage, for which the original interpolation method did not appropriately correct RT shifts. Although further investigation would be required for more types of severe shifts, this study shows that the developed method is useful for correcting RT shifts with GC×GC-HRTOFMS.

Simulating Gas-Liquid-Water Partitioning and Fluid Properties of Petroleum under Pressure: Implications for Deep-Sea Blowouts.

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.

GC×GC Quantification of Priority and Emerging Nonpolar Halogenated Micropollutants in All Types of Wastewater Matrices: Analysis Methodology, Chemical Occurrence, and Partitioning.

We report the development and validation of a method to detect and quantify diverse nonpolar halogenated micropollutants in wastewater treatment plant (WWTP) influent, effluent, primary sludge, and secondary sludge matrices (including both the liquid and particle phases) by comprehensive two-dimensional gas chromatography (GC×GC) coupled to micro- electron capture detector (µECD). The 59 target analytes included toxaphenes, polychlorinated naphthalenes, organochlorine pesticides, polychlorinated biphenyls, polybrominated diphenyl ethers, and emerging persistent and bioaccumulative chemicals. The method is robust for a wide range of nonpolar halogenated micropollutants in all matrices. For most analytes, recoveries fell between 70% and 130% in all matrix types. GC×GC-µECD detections of several target analytes were confirmed qualitatively by further analysis with GC×GC coupled to electron capture negative chemical ionization-time-of-flight mass spectrometry (ENCI-TOFMS). We then quantified the concentrations and apparent organic solid-water partition coefficients (Kp) of target micropollutants in samples from a municipal WWTP in Switzerland. Several analyzed pollutants exhibited a high frequency of occurrence in WWTP stream samples, including octachloronaphthalene, PCB-44, PCB-52, PCB-153, PCB-180, several organochlorine pesticides, PBDE-10, PBDE-28, PBDE-116, musk tibetene, and pentachloronitrobenzene. Our results suggest that sorption to dissolved organic carbon (DOC) can contribute substantially to the apparent solids-liquid distribution of hydrophobic micropollutants in WWTP streams.

Analyte quantification with comprehensive two-dimensional gas chromatography: assessment of methods for baseline correction, peak delineation, and matrix effect elimination for real samples.

Comprehensive two-dimensional gas chromatography (GC×GC) is used widely to separate and measure organic chemicals in complex mixtures. However, approaches to quantify analytes in real, complex samples have not been critically assessed. We quantified 7 PAHs in a certified diesel fuel using GC×GC coupled to flame ionization detector (FID), and we quantified 11 target chlorinated hydrocarbons in a lake water extract using GC×GC with electron capture detector (µECD), further confirmed qualitatively by GC×GC with electron capture negative chemical ionization time-of-flight mass spectrometer (ENCI-TOFMS). Target analyte peak volumes were determined using several existing baseline correction algorithms and peak delineation algorithms. Analyte quantifications were conducted using external standards and also using standard additions, enabling us to diagnose matrix effects. We then applied several chemometric tests to these data. We find that the choice of baseline correction algorithm and peak delineation algorithm strongly influence the reproducibility of analyte signal, error of the calibration offset, proportionality of integrated signal response, and accuracy of quantifications. Additionally, the choice of baseline correction and the peak delineation algorithm are essential for correctly discriminating analyte signal from unresolved complex mixture signal, and this is the chief consideration for controlling matrix effects during quantification. The diagnostic approaches presented here provide guidance for analyte quantification using GC×GC.

First day of an oil spill on the open sea: early mass transfers of hydrocarbons to air and water.

During the first hours after release of petroleum at sea, crude oil hydrocarbons partition rapidly into air and water. However, limited information is available about very early evaporation and dissolution processes. We report on the composition of the oil slick during the first day after a permitted, unrestrained 4.3 m(3) oil release conducted on the North Sea. Rapid mass transfers of volatile and soluble hydrocarbons were observed, with >50% of ≤C17 hydrocarbons disappearing within 25 h from this oil slick of <10 km(2) area and <10 µm thickness. For oil sheen, >50% losses of ≤C16 hydrocarbons were observed after 1 h. We developed a mass transfer model to describe the evolution of oil slick chemical composition and water column hydrocarbon concentrations. The model was parametrized based on environmental conditions and hydrocarbon partitioning properties estimated from comprehensive two-dimensional gas chromatography (GC×GC) retention data. The model correctly predicted the observed fractionation of petroleum hydrocarbons in the oil slick resulting from evaporation and dissolution. This is the first report on the broad-spectrum compositional changes in oil during the first day of a spill at the sea surface. Expected outcomes under other environmental conditions are discussed, as well as comparisons to other models.

Mapping environmental partitioning properties of nonpolar complex mixtures by use of GC × GC.

Comprehensive two-dimensional gas chromatography (GC × GC) is effective for separating and quantifying nonpolar organic chemicals in complex mixtures. Here we present a model to estimate 11 environmental partitioning properties for nonpolar analytes based on GC × GC chromatogram retention time information. The considered partitioning properties span several phases including pure liquid, air, water, octanol, hexadecane, particle natural organic matter, dissolved organic matter, and organism lipids. The model training set and test sets are based on a literature compilation of 648 individual experimental partitioning property data. For a test set of 50 nonpolar environmental contaminants, predicted partition coefficients exhibit root-mean-squared errors ranging from 0.19 to 0.48 log unit, outperforming Abraham-type solvation models for the same chemical set. The approach is applicable to nonpolar organic chemicals containing C, H, F, Cl, Br, and I, having boiling points ≤402 °C. The presented model is calibrated, easy to apply, and requires the user only to identify a small set of known analytes that adapt the model to the GC × GC instrument program. The analyst can thus map partitioning property estimates onto GC × GC chromatograms of complex mixtures. For example, analyzed nonpolar chemicals can be screened for long-range transport potential, aquatic bioaccumulation potential, arctic contamination potential, and other characteristic partitioning behaviors.

Resolving biodegradation patterns of persistent saturated hydrocarbons in weathered oil samples from the Deepwater Horizon disaster.

Biodegradation plays a major role in the natural attenuation of oil spills. However, limited information is available about biodegradation of different saturated hydrocarbon classes in surface environments, despite that oils are composed mostly of saturates, due to the limited ability of conventional gas chromatography (GC) to resolve this compound group. We studied eight weathered oil samples collected from four Gulf of Mexico beaches 12-19 months after the Deepwater Horizon disaster. Using comprehensive two-dimensional gas chromatography (GC × GC), we successfully separated, identified, and quantified several distinct saturates classes in these samples. We find that saturated hydrocarbons eluting after n-C22 dominate the GC-amenable fraction of these weathered samples. This compound group represented 8-10%, or 38-68 thousand metric tons, of the oil originally released from Macondo well. Saturates in the n-C22 to n-C29 elution range were found to be partly biodegraded, but to different relative extents, with ease of biodegradation decreasing in the following order: n-alkanes > methylalkanes and alkylcyclopentanes+alkylcyclohexanes > cyclic and acyclic isoprenoids. We developed a new quantitative index designed to characterize biodegradation of >n-C22 saturates. These results shed new light onto the environmental fate of these persistent, hydrophobic, and mostly overlooked compounds in the unresolved complex mixtures (UCM) of weathered oils.

Oxygenated weathering products of Deepwater Horizon oil come from surprising precursors.

Following the release of crude oil from the Macondo well in 2010, a wide range of weathering processes acted on the spilled oil. A recent study revealed that samples from this spill were oxidized into oxygenated hydrocarbons (OxHC) comprising more than 50% of the extracted hydrocarbons. The precursors of these compounds were not identified despite using a wide range of analytical tools, including gas chromatography (GC). To search for these precursors, over 40 samples were analyzed by comprehensive two-dimensional gas chromatography (GC×GC), one of the largest studies of its kind to date. Partial least squares regression was employed to elucidate the GC×GC peaks that could be the precursors of OxHC in our samples. We found that the formation of OxHC correlated with the disappearance of saturated hydrocarbons, including alkylcyclopentanes, alkyl cyclohexanes, alkylated bicyclic saturated compounds, tricyclic terpanpoids, and alkylbenzenes. These results indicate a previously under-reported chemodynamic process in oil spill weathering.

Robust algorithm for aligning two-dimensional chromatograms.

Comprehensive two-dimensional gas chromatography (GC × GC) chromatograms typically exhibit run-to-run retention time variability. Chromatogram alignment is often a desirable step prior to further analysis of the data, for example, in studies of environmental forensics or weathering of complex mixtures. We present a new algorithm for aligning whole GC × GC chromatograms. This technique is based on alignment points that have locations indicated by the user both in a target chromatogram and in a reference chromatogram. We applied the algorithm to two sets of samples. First, we aligned the chromatograms of twelve compositionally distinct oil spill samples, all analyzed using the same instrument parameters. Second, we applied the algorithm to two compositionally distinct wastewater extracts analyzed using two different instrument temperature programs, thus involving larger retention time shifts than the first sample set. For both sample sets, the new algorithm performed favorably compared to two other available alignment algorithms: that of Pierce, K. M.; Wood, Lianna F.; Wright, B. W.; Synovec, R. E. Anal. Chem.2005, 77, 7735-7743 and 2-D COW from Zhang, D.; Huang, X.; Regnier, F. E.; Zhang, M. Anal. Chem.2008, 80, 2664-2671. The new algorithm achieves the best matches of retention times for test analytes, avoids some artifacts which result from the other alignment algorithms, and incurs the least modification of quantitative signal information.