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  • 1
    Publication Date: 2022-05-25
    Description: Author Posting. © The Oceanography Society, 2016. This article is posted here by permission of The Oceanography Society for personal use, not for redistribution. The definitive version was published in Oceanography 29, no. 3 (2016): 76–87, doi:10.5670/oceanog.2016.72.
    Description: Detecting oil in the northern Gulf of Mexico following the Deepwater Horizon oil spill presented unique challenges due to the spatial and temporal extent of the spill and the subsequent dilution of oil in the environment. Over time, physical, chemical, and biological processes altered the composition of the oil, further complicating its detection. Reservoir fluid, containing gas and oil, released from the Macondo well was detected in surface and subsurface environments. Oil monitoring during and after the spill required a variety of technologies, including nimble adaptation of techniques developed for non-oil-related applications. The oil detection technologies employed varied in sensitivity, selectivity, strategy, cost, usability, expertise of user, and reliability. Innovative technologies ranging from remote sensing to laboratory analytical techniques were employed and produced new information relevant to oil spill detection, including the chemical characterization, the dispersion effectiveness, and the detection limits of oil. The challenge remains to transfer these new technologies to oil spill responders so that detection of oil following a spill can be improved.
    Description: This research was made possible in part by grants from the Gulf Research Program (to HKW); NSF OCE-1333148 (to CMR); and the Gulf of Mexico Research Initiative supporting the ECOGIG-2 consortium (to IRM), the C-IMAGE consortium (to CMR), the DEEP-C consortium (to CMR), and an RFP-II grant (to HKW).
    Repository Name: Woods Hole Open Access Server
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  • 2
    Publication Date: 2022-05-25
    Description: Author Posting. © The Oceanography Society, 2016. This article is posted here by permission of The Oceanography Society for personal use, not for redistribution. The definitive version was published in Oceanography 29, no. 3 (2016): 126–135, doi:10.5670/oceanog.2016.77.
    Description: Crude oil is a complex mixture of many thousands of mostly hydrocarbon and nitrogen-, sulfur-, and oxygen-containing compounds with molecular weights ranging from below 70 Da to well over 2,000 Da. When this complex mixture enters the environment from spills, ruptures, blowouts, or seeps, it undergoes a continuous series of compositional changes that result from a process known as weathering. Spills of petroleum involving human activity generally result in more rapid input of crude oil or refined products (diesel, gasoline, heavy fuel oil, and diluted bitumens) to the marine system than do natural processes and urban runoffs. The primary physicochemical processes involved in weathering include evaporation, dissolution, emulsification, dispersion, sedimentation/flocculation, microbial degradation, and photooxidation.
    Description: The authors of this article received funding from the Gulf of Mexico Research Initiative (data are publicly available through the Gulf of Mexico Research Initiative Information & Data Cooperative [GRIIDC] at https://data.gulfresearchinitiative.org) and the National Science Foundation (CHE-1507295 and OSE-1333148).
    Repository Name: Woods Hole Open Access Server
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  • 3
    Publication Date: 2022-05-25
    Description: Author Posting. © The Author(s), 2017. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Journal of the American Oil Chemists' Society 94 (2017): 831-840, doi: 10.1007/s11746-017-2997-8.
    Description: Polyunsaturated long-chain alkenones are a unique class of lipids biosynthesized in significant quantities (up to 20% of cell carbon) by several algae including the industrially grown marine microalgae Isochrysis. Alkenone structures are characterized by a long linear carbon-chain (35-40 carbons) with one to four trans-double bonds and terminating in a methyl or ethyl ketone. Alkenones were extracted and isolated from commercially obtained Isochrysis biomass and then subjected to cross-metathesis (CM) with methyl acrylate or acrylic acid using the Hoveyda-Grubbs metathesis initiator. Within 1 h at room temperature alkenones were consumed, however complete fragmentation (i.e. conversion to the smallest subunits by double bond cleavage) required up to 16 h. Analysis of the reaction mixture by gas chromatography and comprehensive two-dimensional gas chromatography revealed a predictable product mixture consisting primarily of long-chain (mostly C17) acids (or methyl esters from CM with methyl acrylate) and diacids (or diesters), along with smaller amounts (~5%) of the honey bee “queen substance” (E)-9-oxo-decenoic acid. Together, these compounds comprise a diverse mixture of valuable chemicals that includes surfactants, monomers, and an agriculturally relevant bee pheromone.
    Description: This work was supported by the National Science Foundation (CHE- 1151492) and through a private donation from friends of WHOI.
    Keywords: Algae ; Isochrysis ; Alkenones ; Metathesis ; Surfactants ; Polymers ; Pheromones
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
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  • 4
    Publication Date: 2022-05-25
    Description: © The Author(s), 2017. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Ecology and Society 22 (2017): 18, doi:10.5751/ES-09246-220218.
    Description: As large-scale environmental disasters become increasingly frequent and more severe globally, people and organizations that prepare for and respond to these crises need efficient and effective ways to integrate sound science into their decision making. Experience has shown that integrating nongovernmental scientific expertise into disaster decision making can improve the quality of the response, and is most effective if the integration occurs before, during, and after a crisis, not just during a crisis. However, collaboration between academic, government, and industry scientists, decision makers, and responders is frequently difficult because of cultural differences, misaligned incentives, time pressures, and legal constraints. Our study addressed this challenge by using the Deep Change Method, a design methodology developed by Stanford ChangeLabs, which combines human-centered design, systems analysis, and behavioral psychology. We investigated underlying needs and motivations of government agency staff and academic scientists, mapped the root causes underlying the relationship failures between these two communities based on their experiences, and identified leverage points for shifting deeply rooted perceptions that impede collaboration. We found that building trust and creating mutual value between multiple stakeholders before crises occur is likely to increase the effectiveness of problem solving. We propose a solution, the Science Action Network, which is designed to address barriers to scientific collaboration by providing new mechanisms to build and improve trust and communication between government administrators and scientists, industry representatives, and academic scientists. The Science Action Network has the potential to ensure cross-disaster preparedness and science-based decision making through novel partnerships and scientific coordination.
    Description: The authors thank the David and Lucile Packard Foundation for a grant to undertake this project and enable participation of a wide range of participants and interviewees. We thank the Center for Ocean Solutions and ChangeLabs for their oversight and support.
    Keywords: Deepwater Horizon ; Disaster response ; Human-centered design ; Scientific collaboration ; Systems analysis
    Repository Name: Woods Hole Open Access Server
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  • 5
    Publication Date: 2022-05-25
    Description: Author Posting. © The Author(s), 2015. 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 American 112 (2015): 13184-13189, doi: 10.1073/pnas.1511474112 .
    Description: Hundreds of organic chemicals are utilized during natural gas extraction via high volume hydraulic fracturing (HVHF). However, it is unclear if these chemicals, injected into deep shale horizons, reach shallow groundwater aquifers and impact local water quality, either from deep underground injection sites or from the surface or shallow subsurface. Here, we report detectable levels of organic compounds in shallow groundwater samples from private residential wells overlying the Marcellus Shale in northeastern Pennsylvania. Analyses of purgeable and extractable organic compounds from 64 groundwater samples revealed trace levels of volatile organic compounds, well below the Environmental Protection Agency’s maximum contaminant levels, and low levels of both gasoline range (GRO; 0-8 ppb) and diesel range organic compounds (DRO; 0-157 ppb). A compound-specific analysis revealed the presence of bis(2-ethylhexyl)phthalate, which is a disclosed HVHF additive, that was notably absent in a representative geogenic water sample and field blanks. Pairing these analyses with 1) inorganic chemical fingerprinting of deep saline groundwater, 2) characteristic noble gas isotopes, and 3) spatial relationships between active shale gas extraction wells and wells with disclosed environmental health and safety (EHS) violations, we differentiate between a chemical signature associated with naturally occurring saline groundwater and a one associated with alternative anthropogenic routes from the surface (e.g., accidental spills or leaks). The data support a transport mechanism of DRO to groundwater via accidental release of fracturing fluid chemicals derived from the surface rather than subsurface flow of these fluids from the underlying shale formation.
    Description: The authors thank Duke University’s Pratt School of Engineering and the National Science Foundation’s CBET Grant Number 1336702 and NSF EAGER (EAR-1249255) for financial support.
    Description: 2016-04-12
    Keywords: Hydrophobic organic compounds ; Groundwater ; High volume hydraulic fracturing ; Natural gas extraction ; Transport mechanisms
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
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  • 6
    Publication Date: 2022-05-25
    Description: © The Author(s), 2016. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Chemistry Central Journal 10 (2016): 75, doi:10.1186/s13065-016-0211-y.
    Description: Comprehensive two-dimensional gas chromatography (GC×GC) provides high-resolution separations across hundreds of compounds in a complex mixture, thus unlocking unprecedented information for intricate quantitative interpretation. We exploit this compound diversity across the (GC×GC) topography to provide quantitative compound-cognizant interpretation beyond target compound analysis with petroleum forensics as a practical application. We focus on the (GC×GC) topography of biomarker hydrocarbons, hopanes and steranes, as they are generally recalcitrant to weathering. We introduce peak topography maps (PTM) and topography partitioning techniques that consider a notably broader and more diverse range of target and non-target biomarker compounds compared to traditional approaches that consider approximately 20 biomarker ratios. Specifically, we consider a range of 33–154 target and non-target biomarkers with highest-to-lowest peak ratio within an injection ranging from 4.86 to 19.6 (precise numbers depend on biomarker diversity of individual injections). We also provide a robust quantitative measure for directly determining “match” between samples, without necessitating training data sets. We validate our methods across 34 (GC×GC) injections from a diverse portfolio of petroleum sources, and provide quantitative comparison of performance against established statistical methods such as principal components analysis (PCA). Our data set includes a wide range of samples collected following the 2010 Deepwater Horizon disaster that released approximately 160 million gallons of crude oil from the Macondo well (MW). Samples that were clearly collected following this disaster exhibit statistically significant match (99.23±1.66)% using PTM-based interpretation against other closely related sources. PTM-based interpretation also provides higher differentiation between closely correlated but distinct sources than obtained using PCA-based statistical comparisons. In addition to results based on this experimental field data, we also provide extentive perturbation analysis of the PTM method over numerical simulations that introduce random variability of peak locations over the (GC×GC) biomarker ROI image of the MW pre-spill sample (sample #1 in Additional file 4: Table S1). We compare the robustness of the cross-PTM score against peak location variability in both dimensions and compare the results against PCA analysis over the same set of simulated images. Detailed description of the simulation experiment and discussion of results are provided in Additional file 1: Section S8. We provide a peak-cognizant informational framework for quantitative interpretation of (GC×GC) topography. Proposed topographic analysis enables (GC×GC) forensic interpretation across target petroleum biomarkers, while including the nuances of lesser-known non-target biomarkers clustered around the target peaks. This allows potential discovery of hitherto unknown connections between target and non-target biomarkers.
    Description: This research was made possible in part by a grant from the Gulf of Mexico Research Initiative (GoMRI-015), and the DEEP-C consortium, and in part by NSF Grants OCE-0969841 and RAPID OCE-1043976 as well as a WHOI interdisciplinary study award.
    Repository Name: Woods Hole Open Access Server
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  • 7
    Publication Date: 2022-05-25
    Description: © The Author(s), 2018. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Cosmetics 5 (2018): 34, doi:10.3390/cosmetics5020034.
    Description: The move toward green, sustainable, natural products has been growing in the cosmetic and personal care industry. Ingredients derived from marine organisms and algae are present in many cosmetic products. In this study, a new green ingredient, a wax (i.e., long-chain alkenones) derived from Isochyrsis sp., was evaluated as an alternative for cosmetic waxes. First, the melting point was determined (71.1–77.4 °C), then the alkenones’ thickening capability in five emollients was evaluated and compared to microcrystalline wax and ozokerite. Alkenones were compatible with three emollients and thickened the emollients similarly to the other waxes. Then, lipsticks and lip balms were formulated with and without alkenones. All products remained stable at room temperature for 10 weeks. Lipstick formulated with alkenones was the most resistant to high temperature. Finally, alkenones were compared to three cosmetic thickening waxes in creams. Viscosity, rheology, and stability of the creams were evaluated. All creams had a gel-like behavior. Both viscosity and storage modulus increased in the same order: cream with alkenones 〈 cetyl alcohol 〈 stearic acid 〈 glyceryl monostearate. Overall, alkenones’ performance was comparable to the other three waxes. Alkenones can thus offer a potential green choice as a new cosmetic structuring agent.
    Description: This research was funded by the Washington Research Foundation and a private donor from friends of the Woods Hole Oceanographic Institution, grant number N-126478.
    Keywords: Alkenones ; Isochrysis sp. ; Lipstick ; Lip balm ; Emulsion ; Cosmetic ; Personal care ; Skin care
    Repository Name: Woods Hole Open Access Server
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  • 8
    Publication Date: 2022-05-25
    Description: Author Posting. © American Chemical Society, 2018. This is an open access article published under an ACS AuthorChoice License. The definitive version was published in Environmental Science and Technology Letters 5 (2018): 226–231, doi:10.1021/acs.estlett.8b00084.
    Description: Chemical dispersants are one of many tools used to mitigate the overall environmental impact of oil spills. In principle, dispersants break up floating oil into small droplets that disperse into the water column where they are subject to multiple fate and transport processes. The effectiveness of dispersants typically decreases as oil weathers in the environment. This decrease in effectiveness is often attributed to evaporation and emulsification, with the contribution of photochemical weathering assumed to be negligible. Here, we aim to test this assumption using Macondo well oil released during the Deepwater Horizon spill as a case study. Our results indicate that the effects of photochemical weathering on Deepwater Horizon oil properties and dispersant effectiveness can greatly outweigh the effects of evaporative weathering. The decrease in dispersant effectiveness after light exposure was principally driven by the decreased solubility of photo-oxidized crude oil residues in the solvent system that comprises COREXIT EC9500A. Kinetic modeling combined with geospatial analysis demonstrated that a considerable fraction of aerial applications targeting Deepwater Horizon surface oil had low dispersant effectiveness. Collectively, the results of this study challenge the paradigm that photochemical weathering has a negligible impact on the effectiveness of oil spill response and provide critical insights into the “window of opportunity” to apply chemical dispersants in response to oil spills in sunlit waters.
    Description: This work was supported, in part, by National Science Foundation Grant OCE-1333148, Gulf of Mexico Research Initiative Grants 015, SA 16-30, the DEEP-C consortium, and the Clark Family Foundation, Inc. EPA funding was provided to R.N.C. from the Oil Spill Liability Trust Fund.
    Repository Name: Woods Hole Open Access Server
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  • 9
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2015. 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: Oceans 120 (2015): 7300–7315, doi:10.1002/2015JC011093.
    Description: Releases of hydrocarbons from oil spills have large environmental impacts in both the ocean and atmosphere. Oil evaporation is not simply a mechanism of mass loss from the ocean, as it also causes production of atmospheric pollutants. Monitoring atmospheric emissions from oil spills must include a broad range of volatile organic compounds (VOC), including intermediate-volatile and semivolatile compounds (IVOC, SVOC), which cause secondary organic aerosol (SOA) and ozone production. The Deepwater Horizon (DWH) disaster in the northern Gulf of Mexico during Spring/Summer of 2010 presented a unique opportunity to observe SOA production due to an oil spill. To better understand these observations, we conducted measurements and modeled oil evaporation utilizing unprecedented comprehensive composition measurements, achieved by gas chromatography with vacuum ultraviolet time of flight mass spectrometry (GC-VUV-HR-ToFMS). All hydrocarbons with 10–30 carbons were classified by degree of branching, number of cyclic rings, aromaticity, and molecular weight; these hydrocarbons comprise ∼70% of total oil mass. Such detailed and comprehensive characterization of DWH oil allowed bottom-up estimates of oil evaporation kinetics. We developed an evaporative model, using solely our composition measurements and thermodynamic data, that is in excellent agreement with published mass evaporation rates and our wind-tunnel measurements. Using this model, we determine surface slick samples are composed of oil with a distribution of evaporative ages and identify and characterize probable subsurface transport of oil.
    Description: Funded by Gulf of Mexico Research Initiative
    Description: 2016-05-09
    Keywords: Deepwater Horizon disaster ; Comprehensive gas chromatography with vacuum ultraviolet ionization mass spectrometry ; Evaporative oil weathering ; Secondary organic aerosol
    Repository Name: Woods Hole Open Access Server
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  • 10
    Publication Date: 2022-05-26
    Description: Author Posting. © American Geophysical Union, [year]. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 43 (2016): 5098–5108, doi:10.1002/2016GL069253.
    Description: Pyrogenic carbon (PyC) is a collective term for carbon-rich residues comprised of a continuum of products arising from biomass burning and fossil-fuel combustion. PyC is ubiquitous in the environment where it can be transported by wind and water before being deposited in aquatic sediments. We compare results from four different methods used to trace PyC that were applied to a high-temporal resolution sedimentary record in order to constrain changes in PyC concentrations and fluxes over the past ~250 years. We find markedly discordant records for different PyC tracers, particularly during the preindustrial age, implying different origins and modes of supply of sedimentary PyC. In addition to providing new insights into the composition of sedimentary combustion products, this study reveals that elucidation of past combustion processes and development of accurate budgets of PyC production and deposition on local to regional scales requires careful consideration of both source characteristics and transport processes.
    Description: UZH; NSF Grant Numbers: OCE-9708478, CHE-0089172
    Description: 2016-11-30
    Keywords: Decoupled pyrogenic carbon records ; Aquatic sediments ; Organic carbon cycling ; Local and regional sources ; Transport pathways
    Repository Name: Woods Hole Open Access Server
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