Jonas Gros

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.

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.

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.

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.

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.

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

Significance Environmental risks posed by deep-sea petroleum releases are difficult to predict and assess. We developed a physical model of the buoyant jet of petroleum liquid droplets and gas bubbles gushing into the deep sea, coupled with simulated liquid–gas equilibria and aqueous dissolution kinetics of petroleum compounds, for the 2010 Deepwater Horizon disaster. Simulation results are validated by comparisons with extensive observation data collected in the sea and atmosphere near the release site. Simulations predict that chemical dispersant, injected at the wellhead to mitigate environmental harm, increased the entrapment of volatile compounds in the deep sea and thereby improved air quality at the sea surface. Subsea dispersant injection thus lowered human health risks and accelerated response during the intervention. 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.

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.

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 Henrys 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.

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