ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

Figure 1Loading Img

Deepwater Horizon Oil in Gulf of Mexico Waters after 2 Years: Transformation into the Dissolved Organic Matter Pool

View Author Information
Department of Geological Sciences, University of Florida, Post Office Box 112120, Gainesville, Florida 32611-2120, United States
Department of Marine, Earth, and Atmospheric Sciences, North Carolina State University, Raleigh, North Carolina 27695, United States
§ Department of Oceanography, Texas A&M University, College Station, Texas 77843, United States
School of Freshwater Sciences, University of Wisconsin—Milwaukee, 600 East Greenfield Avenue, Milwaukee, Wisconsin 53204, United States
*Telephone: 352-392-6138. Fax: 352-392-9294. E-mail: [email protected]
Cite this: Environ. Sci. Technol. 2014, 48, 16, 9288–9297
Publication Date (Web):August 1, 2014
Copyright © 2014 American Chemical Society

    Article Views





    Read OnlinePDF (3 MB)
    Supporting Info (1)»


    Abstract Image

    Recent work has shown the presence of anomalous dissolved organic matter (DOM), with high optical yields, in deep waters 15 months after the Deepwater Horizon (DWH) oil spill in the Gulf of Mexico (GOM). Here, we continue to use the fluorescence excitation–emission matrix (EEM) technique coupled with parallel factor analysis (PARAFAC) modeling, measurements of bulk organic carbon, dissolved inorganic carbon (DIC), oil indices, and other optical properties to examine the chemical evolution and transformation of oil components derived from the DWH in the water column of the GOM. Seawater samples were collected from the GOM during July 2012, 2 years after the oil spill. This study shows that, while dissolved organic carbon (DOC) values have decreased since just after the DWH spill, they remain higher at some stations than typical deep-water values for the GOM. Moreover, we continue to observe fluorescent DOM components in deep waters, similar to those of degraded oil observed in lab and field experiments, which suggest that oil-related fluorescence signatures, as part of the DOM pool, have persisted for 2 years in the deep waters. This supports the notion that some oil-derived chromophoric dissolved organic matter (CDOM) components could still be identified in deep waters after 2 years of degradation, which is further supported by the lower DIC and partial pressure of carbon dioxide (pCO2) associated with greater amounts of these oil-derived components in deep waters, assuming microbial activity on DOM in the current water masses is only the controlling factor of DIC and pCO2 concentrations.

    Supporting Information

    Jump To

    Spatial plot of DOC concentrations for July 2012 GOM deep-water samples (Figure S1), DOC profiles for July 2012 sampling locations (Figure S2), absorption spectra of deep-water samples (Figure S3), comparisons to OpenFluor PARAFAC models (Table S1), PARAFAC comparison to Zhou et al. model (Figure S4), and PCA of Fmax values from PARAFAC model for 2010/2012 (Figure S5). This material is available free of charge via the Internet at

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

    Cited By

    This article is cited by 59 publications.

    1. Taylor J. Glattke, Martha L. Chacón-Patiño, Alan G. Marshall, Ryan P. Rodgers. Maltene and Asphaltene Contributions to the Formation of Water-Soluble Emerging Contaminants from Photooxidation of Paving Materials. Energy & Fuels 2022, 36 (21) , 13060-13072.
    2. Jonas Brünjes, Michael Seidel, Thorsten Dittmar, Jutta Niggemann, Florence Schubotz. Natural Asphalt Seeps Are Potential Sources for Recalcitrant Oceanic Dissolved Organic Sulfur and Dissolved Black Carbon. Environmental Science & Technology 2022, 56 (12) , 9092-9102.
    3. Elizabeth A. Whisenhant, Phoebe Zito, David C. Podgorski, Amy M. McKenna, Zachary C. Redman, Patrick L. Tomco. Unique Molecular Features of Water-Soluble Photo-Oxidation Products among Refined Fuels, Crude Oil, and Herded Burnt Residue under High Latitude Conditions. ACS ES&T Water 2022, 2 (6) , 994-1002.
    4. Amy M. McKenna, Huan Chen, Chad R. Weisbrod, Gregory T. Blakney. Molecular Comparison of Solid-Phase Extraction and Liquid/Liquid Extraction of Water-Soluble Petroleum Compounds Produced through Photodegradation and Biodegradation by FT-ICR Mass Spectrometry. Analytical Chemistry 2021, 93 (10) , 4611-4618.
    5. Phoebe Zito, David C. Podgorski, Tessa Bartges, François Guillemette, J. Alan Roebuck, Jr., Robert G. M. Spencer, Ryan P. Rodgers, Matthew A. Tarr. Sunlight-Induced Molecular Progression of Oil into Oxidized Oil Soluble Species, Interfacial Material, and Dissolved Organic Matter. Energy & Fuels 2020, 34 (4) , 4721-4726.
    6. Phoebe Zito, David C. Podgorski, Joshua Johnson, Huan Chen, Ryan P. Rodgers, François Guillemette, Anne M. Kellerman, Robert G. M. Spencer, Matthew A. Tarr. Molecular-Level Composition and Acute Toxicity of Photosolubilized Petrogenic Carbon. Environmental Science & Technology 2019, 53 (14) , 8235-8243.
    7. David C. Podgorski, Phoebe Zito, Jennifer T. McGuire, Dalma Martinovic-Weigelt, Isabelle M. Cozzarelli, Barbara A. Bekins, Robert G. M. Spencer. Examining Natural Attenuation and Acute Toxicity of Petroleum-Derived Dissolved Organic Matter with Optical Spectroscopy. Environmental Science & Technology 2018, 52 (11) , 6157-6166.
    8. Brian H. Harriman, Phoebe Zito, David C. Podgorski, Matthew A. Tarr, and Joseph M. Suflita . Impact of Photooxidation and Biodegradation on the Fate of Oil Spilled During the Deepwater Horizon Incident: Advanced Stages of Weathering. Environmental Science & Technology 2017, 51 (13) , 7412-7421.
    9. Sabine E.-M. Dvorski, Michael Gonsior, Norbert Hertkorn, Jenny Uhl, Hubert Müller, Christian Griebler, and Philippe Schmitt-Kopplin . Geochemistry of Dissolved Organic Matter in a Spatially Highly Resolved Groundwater Petroleum Hydrocarbon Plume Cross-Section. Environmental Science & Technology 2016, 50 (11) , 5536-5546.
    10. Eurico J. D’Sa, Edward B. Overton, Steven E. Lohrenz, Kanchan Maiti, R. Eugene Turner, and Angelina Freeman . Changing Dynamics of Dissolved Organic Matter Fluorescence in the Northern Gulf of Mexico Following the Deepwater Horizon Oil Spill. Environmental Science & Technology 2016, 50 (10) , 4940-4950.
    11. David C. Podgorski, Jacob Walley, Matthew P. Shields, Deja Hebert, Maxwell L. Harsha, Robert G.M. Spencer, Matthew A. Tarr, Phoebe Zito. Dispersant-enhanced photodissolution of macondo crude oil: A molecular perspective. Journal of Hazardous Materials 2024, 461 , 132558.
    12. Angela Hansen, Tamara Kraus, Matthew Landon, Peter McMahon. Spectral characterization of dissolved organic matter in groundwater to assess mixing with oil-field water near selected oil fields, southern California. Science of The Total Environment 2023, 905 , 166970.
    13. Phoebe Zito, David C. Podgorski, Matthew A. Tarr. Emerging Chemical Methods for Petroleum and Petroleum-Derived Dissolved Organic Matter Following the Deepwater Horizon Oil Spill. Annual Review of Analytical Chemistry 2023, 16 (1) , 429-450.
    14. Dario Omanović, Saša Marcinek, Chiara Santinelli. TreatEEM—A Software Tool for the Interpretation of Fluorescence Excitation-Emission Matrices (EEMs) of Dissolved Organic Matter in Natural Waters. Water 2023, 15 (12) , 2214.
    15. Tao Geng, Yan Wang, Xiao-Li Yin, Wu Chen, Hui-Wen Gu. A Comprehensive Review on the Excitation-Emission Matrix Fluorescence Spectroscopic Characterization of Petroleum-Containing Substances: Principles, Methods, and Applications. Critical Reviews in Analytical Chemistry 2023, 16 , 1-23.
    16. Dongping Liu, Hongjie Gao, Huibin Yu, Yonghui Song. Applying EEM-PARAFAC combined with moving-window 2DCOS and structural equation modeling to characterize binding properties of Cu (II) with DOM from different sources in an urbanized river. Water Research 2022, 227 , 119317.
    17. Yiwei Chen, Yizhen Li, Shaolun Yang, Tsung Yen Chiang, Xiaoying Zhu, Jiangyong Hu. Controlling Biofilm Growth and Its Antibiotic Resistance in Drinking Water by Combined UV and Chlorination Processes. Water 2022, 14 (22) , 3643.
    18. Camille Peers de Nieuwburgh, Jonathan S. Watson, Dominik J. Weiss, Mark A. Sephton. Environmental screening of water associated with shale gas extraction by fluorescence excitation emission matrix. Environmental Science: Water Research & Technology 2022, 8 (10) , 2196-2206.
    19. Xiyu Zhang, Shuning Dong, Pengkang Jin, Jidong Liang, Jian Yang, Yongan Huang. Study on the Migration Law of Dissolved Organic Matter in Mine Water Treatment Station. Water 2022, 14 (20) , 3339.
    20. Shudong Ding, Bingyu Wang, Yuanyuan Feng, Haibin Fu, Yanfang Feng, Huifang Xie, Lihong Xue. Livestock manure-derived hydrochar improved rice paddy soil nutrients as a cleaner soil conditioner in contrast to raw material. Journal of Cleaner Production 2022, 372 , 133798.
    21. Bonnie McDevitt, Aaron M. Jubb, Matthew S. Varonka, Madalyn S. Blondes, Mark A. Engle, Tanya J. Gallegos, Jenna L. Shelton. Dissolved organic matter within oil and gas associated wastewaters from U.S. unconventional petroleum plays: Comparisons and consequences for disposal and reuse. Science of The Total Environment 2022, 838 , 156331.
    22. María Claudia Rincón Remolina, Ziyu Li, Nicolás M. Peleato. Application of machine learning methods for rapid fluorescence-based detection of naphthenic acids and phenol in natural surface waters. Journal of Hazardous Materials 2022, 430 , 128491.
    23. Patrick L. Tomco, Khrystyne N. Duddleston, Adrienne Driskill, Jasmine J. Hatton, Kirsten Grond, Toshia Wrenn, Matthew A. Tarr, David C. Podgorski, Phoebe Zito. Dissolved organic matter production from herder application and in-situ burning of crude oil at high latitudes: Bioavailable molecular composition patterns and microbial community diversity effects. Journal of Hazardous Materials 2022, 424 , 127598.
    24. Lauren Ann Weller, E.A Browne, Jacob D. Hosen, Catherine M. Febria. Fluorescent Properties of Water-Extractable Organic Matter in Low-Gradient, Clay Plain Soils Illustrate Efficacy and Scale of Agricultural Management. SSRN Electronic Journal 2022, 67
    25. Gerardo Gold-Bouchot, Samuel Polis, Lauren Elizabeth Castañon, Mayra Padilla Flores, Alyssa Nicole Alsante, Daniel Conrad Ogilvie Thornton. Chromophoric dissolved organic matter (CDOM) in a subtropical estuary (Galveston Bay, USA) and the impact of Hurricane Harvey. Environmental Science and Pollution Research 2021, 28 (38) , 53045-53057.
    26. Rongting Ji, Lianghu Su, Hu Cheng, Yuan Wang, Ju Min, Mei Chen, Haidong Li, Sujuan Chen, Saier Wang, Guo Yu, Longjiang Zhang, Jiangang Han. Insights into the potential release of dissolved organic matter from different agro-forest waste-derived hydrochars: A pilot study. Journal of Cleaner Production 2021, 319 , 128676.
    27. Lili Lyu, Ge Liu, Yingxin Shang, Zhidan Wen, Junbin Hou, Kaishan Song. Characterization of dissolved organic matter (DOM) in an urbanized watershed using spectroscopic analysis. Chemosphere 2021, 277 , 130210.
    28. Levi G. Oliveira, Kelvin C. Araújo, Matheus C. Barreto, Maria Eugênia P.A. Bastos, Sherlan G. Lemos, Wallace D. Fragoso. Applications of chemometrics in oil spill studies. Microchemical Journal 2021, 166 , 106216.
    29. Kun-Fang Xi, Wei-Fei Hu, De-Chang Li, Shun-Feng Jiang, Hong Jiang. Investigations on the dissolved organic matter leached from oil-contaminated soils by using pyrolysis remediation method. Science of The Total Environment 2021, 776 , 145921.
    30. Laura Logozzo, Maria Tzortziou, Patrick Neale, J. Blake Clark. Photochemical and Microbial Degradation of Chromophoric Dissolved Organic Matter Exported From Tidal Marshes. Journal of Geophysical Research: Biogeosciences 2021, 126 (4)
    31. Benjamin H. Gregson, Boyd A. McKew, Robert D. Holland, Timothy J. Nedwed, Roger C. Prince, Terry J. McGenity. Marine Oil Snow, a Microbial Perspective. Frontiers in Marine Science 2021, 8
    32. David C. Podgorski, Phoebe Zito, Anne M. Kellerman, Barbara A. Bekins, Isabelle M. Cozzarelli, Donald F. Smith, Xiaoyan Cao, Klaus Schmidt-Rohr, Sasha Wagner, Aron Stubbins, Robert G.M. Spencer. Hydrocarbons to carboxyl-rich alicyclic molecules: A continuum model to describe biodegradation of petroleum-derived dissolved organic matter in contaminated groundwater plumes. Journal of Hazardous Materials 2021, 402 , 123998.
    33. Sasha Wagner, Florence Schubotz, Karl Kaiser, Christian Hallmann, Hannelore Waska, Pamela E. Rossel, Roberta Hansman, Marcus Elvert, Jack J. Middelburg, Anja Engel, Thomas M. Blattmann, Teresa S. Catalá, Sinikka T. Lennartz, Gonzalo V. Gomez-Saez, Silvio Pantoja-Gutiérrez, Rui Bao, Valier Galy. Soothsaying DOM: A Current Perspective on the Future of Oceanic Dissolved Organic Carbon. Frontiers in Marine Science 2020, 7
    34. Albertinka J. Murk, David J. Hollander, Shuangling Chen, Chuanmin Hu, Yongxue Liu, Sophie M. Vonk, Patrick T. Schwing, Sherryl Gilbert, Edwin M. Foekema. A Predictive Strategy for Mapping Locations Where Future MOSSFA Events Are Expected. 2020, 355-368.
    35. Haodong Ji, Wenbo Xie, Wen Liu, Xiaona Liu, Dongye Zhao. Sorption of dispersed petroleum hydrocarbons by activated charcoals: Effects of oil dispersants. Environmental Pollution 2020, 256 , 113416.
    36. Jeonghyun Kim, Yeseul Kim, Hyoun-Woo Kang, Suk Hyun Kim, TaeKeun Rho, Dong-Jin Kang. Tracing water mass fractions in the deep western Indian Ocean using fluorescent dissolved organic matter. Marine Chemistry 2020, 218 , 103720.
    37. Aprami Jaggi, Jagoš R. Radović, Lloyd R. Snowdon, Stephen R. Larter, Thomas B.P. Oldenburg. Composition of the dissolved organic matter produced during in situ burning of spilled oil. Organic Geochemistry 2019, 138 , 103926.
    38. Wei Zhang, Yongqiang Zhou, Erik Jeppesen, Liqing Wang, Hongxin Tan, Junyi Zhang. Linking heterotrophic bacterioplankton community composition to the optical dynamics of dissolved organic matter in a large eutrophic Chinese lake. Science of The Total Environment 2019, 679 , 136-147.
    39. Fatemeh S. Mirnaghi, Natalie P. Pinchin, Zeyu Yang, Bruce P. Hollebone, Patrick Lambert, Carl E. Brown. Monitoring of polycyclic aromatic hydrocarbon contamination at four oil spill sites using fluorescence spectroscopy coupled with parallel factor-principal component analysis. Environmental Science: Processes & Impacts 2019, 21 (3) , 413-426.
    40. Liyang Yang, Wei Chen, Wan-E Zhuang, Qiong Cheng, Wenxin Li, Hui Wang, Weidong Guo, Chen-Tung Arthur Chen, Minghua Liu. Characterization and bioavailability of rainwater dissolved organic matter at the southeast coast of China using absorption spectroscopy and fluorescence EEM-PARAFAC. Estuarine, Coastal and Shelf Science 2019, 217 , 45-55.
    41. Stuart C. Painter, Dan J. Lapworth, E. Malcolm S. Woodward, Silke Kroeger, Chris D. Evans, Daniel J. Mayor, Richard J. Sanders. Terrestrial dissolved organic matter distribution in the North Sea. Science of The Total Environment 2018, 630 , 630-647.
    42. Thomas S. Bianchi, Xingqian Cui, Neal E. Blair, David J. Burdige, Timothy I. Eglinton, Valier Galy. Centers of organic carbon burial and oxidation at the land-ocean interface. Organic Geochemistry 2018, 115 , 138-155.
    43. Alba María Martínez-Pérez, Mar Nieto-Cid, Helena Osterholz, Teresa S. Catalá, Isabel Reche, Thorsten Dittmar, Xosé Antón Álvarez-Salgado. Linking optical and molecular signatures of dissolved organic matter in the Mediterranean Sea. Scientific Reports 2017, 7 (1)
    44. Guowei Wang, Bin Yu, Shiguo Chen, Hiroshi Uyama. Template-free synthesis of polystyrene monoliths for the removal of oil-in-water emulsion. Scientific Reports 2017, 7 (1)
    45. Haoshuai Li, Long Meng, Tiantian Shen, Jianrui Zhang, Mutai Bao, Peiyan Sun. The formation process and responsive impacts of single oil droplet in submerged process. Marine Pollution Bulletin 2017, 124 (1) , 139-146.
    46. Lydia Babcock-Adams, Jeffrey P. Chanton, Samantha B. Joye, Patricia M. Medeiros. Hydrocarbon composition and concentrations in the Gulf of Mexico sediments in the 3 years following the Macondo well blowout. Environmental Pollution 2017, 229 , 329-338.
    47. Long Meng, Mutai Bao, Peiyan Sun. A new perspective of particle adsorption: Dispersed oil and granular materials interactions in simulated coastal environment. Marine Pollution Bulletin 2017, 122 (1-2) , 100-109.
    48. B. D. Walker, E. R. M. Druffel, J. Kolasinski, B. J. Roberts, X. Xu, B. E. Rosenheim. Stable and radiocarbon isotopic composition of dissolved organic matter in the Gulf of Mexico. Geophysical Research Letters 2017, 44 (16) , 8424-8434.
    49. M Gonnelli, Y Galletti, E Marchetti, L Mercadante, S Retelletti Brogi, A Ribotti, R Sorgente, S Vestri, C Santinelli. Dissolved organic matter dynamics in surface waters affected by oil spill pollution: Results from the Serious Game exercise. Deep Sea Research Part II: Topical Studies in Oceanography 2016, 133 , 88-99.
    50. Jonny Beyer, Hilde C. Trannum, Torgeir Bakke, Peter V. Hodson, Tracy K. Collier. Environmental effects of the Deepwater Horizon oil spill: A review. Marine Pollution Bulletin 2016, 110 (1) , 28-51.
    51. Helen White, Robyn Commy, Ian MacDonald, Christopher Reddy. Methods of Oil Detection in Response to the Deepwater Horizon Oil Spill. Oceanography 2016, 29 (3) , 76-87.
    52. Jorge Nimptsch, Stefan Woelfl, Sebastian Osorio, Jose Valenzuela, Paul Ebersbach, Wolf von Tuempling, Rodrigo Palma, Francisco Encina, David Figueroa, Norbert Kamjunke, Daniel Graeber. Tracing dissolved organic matter (DOM) from land-based aquaculture systems in North Patagonian streams. Science of The Total Environment 2015, 537 , 129-138.
    53. Christian Coelho, Ghislain Guyot. Excitation–Emission Matrices of Fluorescence – EEMF – for the Characterization of Organic Matter of Surface Waters. 2015, 97-115.
    54. Céline Guéguen, Motoyo Itoh, Takashi Kikuchi, Jane Eert, William J. Williams. Variability in dissolved organic matter optical properties in surface waters in the Amerasian Basin. Frontiers in Marine Science 2015, 2
    55. Yina Liu, Elizabeth B. Kujawinski, . Chemical Composition and Potential Environmental Impacts of Water-Soluble Polar Crude Oil Components Inferred from ESI FT-ICR MS. PLOS ONE 2015, 10 (9) , e0136376.
    56. Peng Lin, Laodong Guo. Spatial and vertical variability of dissolved carbohydrate species in the northern Gulf of Mexico following the Deepwater Horizon oil spill, 2010–2011. Marine Chemistry 2015, 174 , 13-25.
    57. Youhei Yamashita, S. Leigh McCallister, Boris P. Koch, Michael Gonsior, Rudolf Jaffé. Dynamics of dissolved organic matter in fjord ecosystems: Contributions of terrestrial dissolved organic matter in the deep layer. Estuarine, Coastal and Shelf Science 2015, 159 , 37-49.
    58. Yaal Lester, Imma Ferrer, E. Michael Thurman, Kurban A. Sitterley, Julie A. Korak, George Aiken, Karl G. Linden. Characterization of hydraulic fracturing flowback water in Colorado: Implications for water treatment. Science of The Total Environment 2015, 512-513 , 637-644.
    59. Zhengzhen Zhou, Laodong Guo, Christopher L. Osburn. Fluorescence EEMs and PARAFAC Techniques in the Analysis of Petroleum Components in the Water Column. 2015, 179-200.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Your Mendeley pairing has expired. Please reconnect