Robert K. Nelson

Composition and fate of gas and oil released to the water column during the Deepwater Horizon oil spill

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 C1-C5 hydrocarbons released to the water column was 1.7 × 1011 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 C1-C5 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.

Impact of the Deepwater Horizon oil spill on a deep-water coral community in the Gulf of Mexico

To assess the potential impact of the Deepwater Horizon oil spill on offshore ecosystems, 11 sites hosting deep-water coral communities were examined 3 to 4 mo after the well was capped. Healthy coral communities were observed at all sites >20 km from the Macondo well, including seven sites previously visited in September 2009, where the corals and communities appeared unchanged. However, at one site 11 km southwest of the Macondo well, coral colonies presented widespread signs of stress, including varying degrees of tissue loss, sclerite enlargement, excess mucous production, bleached commensal ophiuroids, and covering by brown flocculent material (floc). On the basis of these criteria the level of impact to individual colonies was ranked from 0 (least impact) to 4 (greatest impact). Of the 43 corals imaged at that site, 46% exhibited evidence of impact on more than half of the colony, whereas nearly a quarter of all of the corals showed impact to >90% of the colony. Additionally, 53% of these corals’ ophiuroid associates displayed abnormal color and/or attachment posture. Analysis of hopanoid petroleum biomarkers isolated from the floc provides strong evidence that this material contained oil from the Macondo well. The presence of recently damaged and deceased corals beneath the path of a previously documented plume emanating from the Macondo well provides compelling evidence that the oil impacted deep-water ecosystems. Our findings underscore the unprecedented nature of the spill in terms of its magnitude, release at depth, and impact to deep-water ecosystems.

Oil Weathering after the Deepwater Horizon Disaster Led to the Formation of Oxygenated Residues

Following the Deepwater Horizon disaster, the effect of weathering on surface slicks, oil-soaked sands, and oil-covered rocks and boulders was studied for 18 months. With time, oxygen content increased in the hydrocarbon residues. Furthermore, a weathering-dependent increase of an operationally defined oxygenated fraction relative to the saturated and aromatic fractions was observed. This oxygenated fraction made up >50% of the mass of weathered samples, had an average carbon oxidation state of -1.0, and an average molecular formula of (C(5)H(7)O)(n). These oxygenated hydrocarbon residues were devoid of natural radiocarbon, confirming a fossil source and excluding contributions from recent photosynthate. The incorporation of oxygen into the oils hydrocarbons, which we refer to as oxyhydrocarbons, was confirmed from the detection of hydroxyl and carbonyl functional groups and the identification of long chain (C(10)-C(32)) carboxylic acids as well as alcohols. On the basis of the diagnostic ratios of alkanes and polycyclic aromatic hydrocarbons, and the context within which these samples were collected, we hypothesize that biodegradation and photooxidation share responsibility for the accumulation of oxygen in the oil residues. These results reveal that molecular-level transformations of petroleum hydrocarbons lead to increasing amounts of, apparently recalcitrant, oxyhydrocarbons that dominate the solvent-extractable material from oiled samples.

Fallout plume of submerged oil from Deepwater Horizon

Significance Following the sinking of the Deepwater Horizon in the Gulf of Mexico an unprecedented quantity of oil irrupted into the ocean at a depth of 1.5 km. The novelty of this event makes the oil’s subsequent fate in the deep ocean difficult to predict. This work identifies a fallout plume of hydrocarbons from the Macondo Well contaminating the ocean floor over an area of 3,200 km2. Our analysis suggests the oil initially was suspended in deep waters and then settled to the underlying sea floor. The spatial distribution of contamination implicates accelerated settling as an important fate for suspended oil, supports a patchwork mosaic model of oil deposition, and frames ongoing attempts to determine the event’s impact on deep-ocean ecology. The sinking of the Deepwater Horizon in the Gulf of Mexico led to uncontrolled emission of oil to the ocean, with an official government estimate of ∼5.0 million barrels released. Among the pressing uncertainties surrounding this event is the fate of ∼2 million barrels of submerged oil thought to have been trapped in deep-ocean intrusion layers at depths of ∼1,000–1,300 m. Here we use chemical distributions of hydrocarbons in >3,000 sediment samples from 534 locations to describe a footprint of oil deposited on the deep-ocean floor. Using a recalcitrant biomarker of crude oil, 17α(H),21β(H)-hopane (hopane), we have identified a 3,200-km2 region around the Macondo Well contaminated by ∼1.8 ± 1.0 × 106 g of excess hopane. Based on spatial, chemical, oceanographic, and mass balance considerations, we calculate that this contamination represents 4–31% of the oil sequestered in the deep ocean. The pattern of contamination points to deep-ocean intrusion layers as the source and is most consistent with dual modes of deposition: a “bathtub ring” formed from an oil-rich layer of water impinging laterally upon the continental slope (at a depth of ∼900–1,300 m) and a higher-flux “fallout plume” where suspended oil particles sank to underlying sediment (at a depth of ∼1,300–1,700 m). We also suggest that a significant quantity of oil was deposited on the ocean floor outside this area but so far has evaded detection because of its heterogeneous spatial distribution.

Tracking the Weathering of an Oil Spill with Comprehensive Two-Dimensional Gas Chromatography

Comprehensive two-dimensional gas chromatography (GC × GC) was used to investigate the Bouchard 120 oil spill. The latter occurred on April 25, 2003, when the barge Bouchard 120 spilled ∼ 375,000 liters of No. 6 fuel oil into Buzzards Bay, Massachusetts. In order to gain a better understanding of the natural processes affecting the fate of the spilled product, we collected and analyzed oil-covered rocks from Nyes Neck beach in North Falmouth, Massachusetts. Here we discuss the data from samples collected on May 9, 2003, and six months later, on November 23, 2003. Along with standard two-dimensional gas chromatographic analysis, we employed unique data-visualization techniques such as difference, ratio, and addition chromatograms to highlight how evaporation, water washing, and biodegradation weathered the spilled oil. These approaches provide a new perspective to studying oil spills and aid attempts to remediate them.

Recalcitrance and degradation of petroleum biomarkers upon abiotic and biotic natural weathering of Deepwater Horizon oil.

Petroleum biomarkers such as hopanoids, steranes, and triaromatic steroids (TAS) are commonly used to investigate the source and fate of petroleum hydrocarbons in the environment based on the premise that these compounds are resistant to biotic and abiotic degradation. To test the validity of this premise in the context of the Deepwater Horizon disaster, we investigated changes to these biomarkers as induced by natural weathering of crude oil discharged from the Macondo Well (MW). For surface slicks collected from May to June in 2010, and other oiled samples collected on beaches in the northern Gulf of Mexico from July 2010 until August 2012, hopanoids with up to 31 carbons as well as steranes and diasteranes were not systematically affected by weathering processes. In contrast, TAS and C32- to C35-homohopanes were depleted in all samples relative to 17α(H),21β(H)-hopane (C30-hopane). Compared to MW oil, C35-homohopanes and TAS were depleted by 18 ± 10% and 36 ± 20%, respectively, in surface slicks collected from May to June 2010, and by 37 ± 9% and 67 ± 10%, respectively, in samples collected along beaches from April 2011 through August 2012. Based on patterns of relative losses of individual compounds, we hypothesize biodegradation and photooxidation as main degradation processes for homohopanes and TAS, respectively. This study highlights that (i) TAS and homohopanes can be degraded within several years following an oil spill, (ii) the use of homohopanes and TAS for oil spill forensics must account for degradation, and (iii) these compounds provide a window to parse biodegradation and photooxidation during advanced stages of oil weathering.

Expansion of the Analytical Window for Oil Spill Characterization by Ultrahigh Resolution Mass Spectrometry: Beyond Gas Chromatography

Traditional tools for routine environmental analysis and forensic chemistry of petroleum have relied almost exclusively on gas chromatography-mass spectrometry (GC-MS), although many compounds in crude oil (and its transformation products) are not chromatographically separated or amenable to GC-MS due to volatility. To enhance current and future studies on the fate, transport, and fingerprinting of the Macondo well oil released from the 2010 Deepwater Horizon disaster, we created an extensive molecular library of the unadulterated petroleum to compare to a tar ball collected on the beach of Louisiana. We apply ultrahigh resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry to identify compositional changes at the molecular level between native and weathered crude oil samples and reveal enrichment in polar compounds inaccessible by GC-based characterization. The outlined approach provides unprecedented detail with the potential to enhance insight into the environmental fate of spilled oil, improved toxicology, molecular modeling of biotic/abiotic weathering, and comprehensive molecular characterization for petroleum-derived releases. Here, we characterize more than 30,000 acidic, basic, and nonpolar unique neutral elemental compositions for the Macondo well crude oil, to provide an archive for future chemical analyses of the environmental consequences of the oil spill.

Identification of a novel alkenone in Black Sea sediments

Abstract We report the identification of a novel long-chain ketone in Holocene Black Sea sediments. Based on chemical properties, and chromatographic and mass spectrometric characteristics, this compound has been identified as a di-unsaturated C36 ethyl ketone. Further analyses indicated the position and configuration of the double bonds, and the novel alkenone was determined to be hexatriaconta-(16E,21E)-dien-3-one. While this compound is present in only trace quantities in Unit I sediments, it is the most abundant alkenone in portions of Unit II. Its presence thus apparently pre-dates the invasion of Emiliania huxleyi in the Black Sea. The down-core profiles and isotopic compositions suggest that the precursor for the C36:2 alkenone may be distinct from that of the C37-39 alkenones, however the biological origin of this novel compound is presently unknown.

Assessment of photochemical processes in marine oil spill fingerprinting.

Understanding weathering processes plays a critical role in oil spill forensics, which is based on the comparison of the distributions of selected compounds assumed to be recalcitrant and/or have consistent weathering transformations. Yet, these assumptions are based on limited laboratory and oil-spill studies. With access to additional sites that have been oiled by different types of oils and exposures, there is a great opportunity to expand on our knowledge about these transformations. Here, we demonstrate the effects of photooxidation on the overall composition of spilled oils caused by natural and simulated sunlight, and particularly on the often used polycyclic aromatic hydrocarbons (PAHs) and the biomarker triaromatic steranes (TAS). Both laboratory and field data from oil released from the Macondo well oil following the Deepwater Horizon disaster (2010), and heavy fuel-oil from the Prestige tanker spill (2002) have been obtained to improve the data interpretation of the typical fingerprinting methodology.

Seasonal seawater optical properties of the U.S. Middle Atlantic Bight

Optical properties of seawater in the U.S. Middle Atlantic Bight (MAB) were measured during four cruises spanning 1993–1994. Samples were collected in August and November 1993 and March and April 1994 along a cruise track extending from Delaware Bay to the Sargasso Sea. Each sample was analyzed for colored dissolved organic matter (CDOM) and particulate absorption and chlorophyll a (chl a). In situ attenuation and reflectance were also measured at selected stations using underwater spectroradiometers. The overall seasonal and spatial ranges for CDOM and particulate absorption (442 nm) and chl a concentration were 0.02–0.41 m−1, 0.01–0.49 m−1, and 0.07–9.4 mg m−3, respectively. CDOM absorption ranged from twofold to threefold between seasons on the MAB shelf, whereas particulate absorption ranged from threefold to sevenfold at the same locations. The results indicate that although CDOM absorption often dominated water column light attenuation at chl a absorbing wavelengths (e.g., 442 nm), chl a could be estimated from in situ reflectance spectra with an average error of ±20% using a relationship previously determined for coastal and open ocean waters. It appears that reflectances at 442 nm (R442) within the MAB shelf are typically low and invariable and most of the chl a sensitivity is contained in the ratio denominator (R554), resulting in relative insensitivity to CDOM absorption. Furthermore, CDOM absorption could not be explicitly determined using reflectance ratios (R412/R490); rather, the reflectance ratios correlated more closely with total (CDOM plus particulate) absorption.