Search

© 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., 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., 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.

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., 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., This research was supported by NSF grant OCE-1043976 to CR.

Author Posting. © American Geophysical Union, 2004. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 109 (2004): C08S17, doi:10.1029/2003JC002131., The influence of wind stress, small-scale waves, and surface films on air-sea gas exchange at low to moderate wind speeds (<10 m s−1) is examined. Coincident observations of wind stress, heat transfer velocity, surface wave slope, and surface film enrichments were made in coastal and offshore waters south of Cape Cod, New England, in July 1997 as part of the NSF-CoOP Coastal Air-Sea Chemical Fluxes study. Gas transfer velocities have been extrapolated from aqueous heat transfer velocities derived from infrared imagery and direct covariance and bulk heat flux estimates. Gas transfer velocity is found to follow a quadratic relationship with wind speed, which accounts for ~75–77% of the variance but which overpredicts transfer velocity in the presence of surface films. The dependence on wind stress as represented by the friction velocity is also nonlinear, reflecting a wave field-dependent transition between limiting transport regimes. In contrast, the dependence on mean square slope computed for the wave number range of 40–800 rad m−1 is found to be linear and in agreement with results from previous laboratory wind wave studies. The slope spectrum of the small-scale waves and the gas transfer velocity are attenuated in the presence of surface films. Observations over large-scale gradients of biological productivity and dissolved organic matter show that the reduction in slope and transfer velocity are more clearly correlated with surface film enrichments than with bulk organic matter concentrations. The mean square slope parameterization explains ~89–95% of the observed variance in the data and does not overpredict transfer velocities where films are present. While the specific relationships between gas transfer velocity and wind speed or mean square slope vary slightly with the choice of Schmidt number exponent used to scale the heat transfer velocities to gas transfer velocities, the correlation of heat or gas transfer velocity with mean square slope is consistently, Funding for this work was provided by the NSF Coastal Ocean Processes (CoOP) program (OCE-9410534, OCE- 9711285 (WHOI) and OCE-9409222, OCE-9711391(URI)). Additional support for data analysis was provided by NASA (NAGW-2431, JPL Contract 961425). Partial funding was also provided by the German Science Foundation (DFG) through the DFG research unit FOR240: Image Sequence Analysis to Investigate Dynamic Processes.

Every year, natural petroleum seepage emits 0.2-2 Tg of oil to the ocean. Significant oil seepage can build large underwater mounds, consisting of tar deposits with morphologies similar to volcanic lava flows, known as asphalt volcanoes. Such events are typically accompanied by large fluxes of the greenhouse gas methane. Marine sediments from the Santa Barbara basin, California, contain a record of elevated methane concentrations, anoxia and tar deposition during the Pleistocene epoch that had been attributed to dissolution of methane hydrates. However, the region is known to have exhibited oil seepage in the past. Here, we document the discovery of seven extinct asphalt volcanoes off the coast of southern California. The morphology of the deposits and geochemistry of samples taken from the two largest structures supports their classification as asphalt volcanoes, derived from a common source. We estimate that the two structures resulted from seepage of 0.07-0.4 Tg of oil, accompanied by the emission of 0.35-1.8 Tg of methane. Radiocarbon dating of carbonate deposits entrained with the asphalt indicates formation of the volcanoes between 44 and 31 kyr ago. The timing and volume of erupted hydrocarbons from the asphalt structures can explain some or all of the documented methane release and tar accumulation in the Santa Barbara basin during the Pleistocene. © 2010 Macmillan Publishers Limited.

Author Posting. © Springer, 2007. This is the author's version of the work. It is posted here by permission of Springer for personal use, not for redistribution. The definitive version was published in Journal of Radioanalytical and Nuclear Chemistry 273 (2007): 383-393, doi:10.1007/s10967-007-6898-4., A reference material designed for the determination of anthropogenic and natural radionuclides in sediment, IAEA-384 (Fangataufa Lagoon sediment), is described and the results of certification are presented. The material has been certified for 8 radionuclides (40K, 60Co, 155Eu, 230Th, 238U, 238Pu, 239+240Pu and 241Am). Information values are given for 12 radionuclides (90Sr, 137Cs, 210Pb (210Po), 226Ra, 228Ra, 232Th, 234U, 235U, 239Pu, 240Pu and 241Pu). Less reported radionuclides include 228Th, 236U, 239Np and 242Pu. The reference material may be used for quality management of radioanalytical laboratories engaged in the analysis of radionuclides in the environment, as well as for the development and validation of analytical methods and for training purposes. The material is available from IAEA in 100 g units.

Comprehensive two-dimensional gas chromatography (GC x 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., Sponsored in part by National Science Foundation Grant no. IIS-0430835 and by EnvironmentalProtection Agency Grant no. R-830393. Prepared in collaboration with Department of Science, United States Coast Guard Academy, New London, CT and the Computer Science & Engineering Department, University of Nebraska, Lincoln, NE. Published in Environmental Forensics, v7, p33-44, 2006. The original document contains color images. All DTIC reproductions will be in black and white.

Author Posting. © The Authors, 2006. This is the author's version of the work. It is posted here by permission of National Academy of Sciences for personal use, not for redistribution. The definitive version was published in Proceedings of the National Academy of Sciences of the United States of America 103 (2006): 13570-13574, doi:10.1073/pnas.0601304103., Marine hydrocarbon seepage emits oil and gas, including methane (~30 Tg CH4/year), to the ocean and atmosphere. Sediments from the California margin contain preserved tar, primarily formed via hydrocarbon weathering at the sea surface. We present a record of variation in the abundance of tar in sediments for the past 32ky, providing evidence for increases in hydrocarbon emissions prior to and during Termination IA (16-14 ka) and again over Termination IB (11-10 ka). Our study provides the first direct evidence for increased hydrocarbon seepage associated with deglacial warming via tar abundance in marine sediments, independent of previous geochemical proxies. Climate-sensitive gas hydrates may modulate thermogenic hydrocarbon seepage during deglaciation., This work has been supported by the U.S. National Science Foundation (OCE-0242041, Kennett; OCE-0447395, Valentine; IIS-0430835, Reddy) and UC Santa Barbara (Graduate Dissertation Fellowship to T. Hill).

The influence of wind stress, small-scale waves, and surface films on air-sea gas exchange at low to moderate wind speeds (<10 m s -1) is examined. Coincident observations of wind stress, heat transfer velocity, surface wave slope, and surface film enrichments were made in coastal and offshore waters south of Cape Cod, New England, in July 1997 as part of the NSF-CoOP Coastal Air-Sea Chemical Fluxes study. Gas transfer velocities have been extrapolated from aqueous heat transfer velocities derived from infrared imagery and direct covariance and bulk heat flux estimates. Gas transfer velocity is found to follow a quadratic relationship with wind speed, which accounts for ∼75-77% of the variance but which overpredicts transfer velocity in the presence of surface films. The dependence on wind stress as represented by the friction velocity is also nonlinear, reflecting a wave field-dependent transition between limiting transport regimes. In contrast, the dependence on mean square slope computed for the wave number range of 40-800 rad m-1 is found to be linear and in agreement with results from previous laboratory wind wave studies. The slope spectrum of the small-scale waves and the gas transfer velocity are attenuated in the presence of surface films. Observations over large-scale gradients of biological productivity and dissolved organic matter show that the reduction in slope and transfer velocity are more clearly correlated with surface film enrichments than with bulk organic matter concentrations. The mean square slope parameterization explains ∼89-95% of the observed variance in the data and does not overpredict transfer velocities where films are present. While the specific relationships between gas transfer velocity and wind speed or mean square slope vary slightly with the choice of Schmidt number exponent used to scale the heat transfer velocities to gas transfer velocities, the correlation of heat or gas transfer velocity with mean square slope is consistentl

The potential role of surface microlayer surfactants in modulating air-sea exchange processes in the low wind regime is examined. Variations in surfactant concentration and surface microlayer enrichments are compared with variations in the small-scale wave slope spectrum on large and small spatial scales over large gradients in biological productivity and organic matter level. Surfactant films are shown to strongly reduce the one-sided omnidirectional wave slope S(k) at wave numbers k = 100 - 400 rad m-1. The degree of reduction is dependent on the excess microlayer surfactant relative to the underlying water rather than bulk surfactant concentration. The observed wave slope reductions imply corresponding reductions in mass and momentum exchange.

Experiments performed in the Pacific and Atlantic Oceans in 1995 and 1997 attempted to measure the short time-scale and small spatial scale variability in the air-sea gas transfer rate. Along with these measurements, physical and chemical parameters known from previous laboratory studies to influence transfer rates were also characterized. These parameters include the atmospheric forcing, the capillary and capillary-gravity wave state, the surface chemical enrichment, and the level of near-surface turbulence. In this contribution we describe the methodologies employed for the measurement campaigns and summarize some general observations resulting from them. Other contributions from the coauthors describe in more detail the specific conclusions derived from the Coastal Ocean Processes (CoOP) field program.