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OIL IN THE -SEA INPUTS, FATES, AND EFFECTS Steering Committee for the Petroleum in the Marine Environment Update Board on Ocean Science and Policy Ocean Sciences Board Commission on Physical Sciences, Mathematics, and Resources National Research Council NATIONAL ACADEMY PRESS Washington, D.C. 1985

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NATIONAL ACADEMY PRESS 2101 Constitution Avenue, NW Washington, DC 20418 NOTICE: The project that is the subject of this report was approved by the Governing Board of the National Research Council, whose members are drawn from the councils of the National Academy of Sciences, the National Academy of Engineering, and the Institute of Medicine. The members of the committee responsible for the report were chosen for their special competences and with regard for appropriate balance. This report has been reviewed by a group other than the authors according to procedures approved by a Report Review Committee consisting of members of the National Academy of Sciences, the National Academy of Engineering, and the Institute of Medicine. The National Research Council was established by the National Academy of Sciences in 1916 to associate the broad community of science and technology with the Academy's purposes of furthering knowledge and of advising the federal government. The Council operates in accordance with general policies determined by the Academy under the authority of its congressional charter of 1863, which establishes the Academy as a private, nonprofit, self-governing membership corporation. The Council has become the principal operating agency of both the National Academy of Sciences and the National Academy of Engineering in the conduct of their services to the government, the public, and the scientific and engineering communities. It is administered jointly by both Academies and the Institute of Medicine. The National Academy of Engineering and the Institute of Medicine were established in 1964 and 1970, respectively, under the charter of the National Academy of Sciences. Library of Congress Catalog Card Number 85-60541 International Standard Book Number 0-309-03479-5 Printed in the United States of America Cover Photograph: Courtesy, Exxon Corporation and American Petroleum Institute Photographic and Film Services.

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Ocean Sciences Board JOHN H. STEELE, Woods Hole Oceanographic Institution, Chairman GUSTAF O.S. ARRHENIUS, Scripps Institution of Oceanography ALBERT W. B. ALLY, Rice University WILLARD BASCOM, Southern California Coastal Water Research Project ROBERT C. BEARDSLEY, Woods Hole Oceanographic Institution KIRK BRYAN, Geophysical Fluid Dynamics Laboratory (NOAA) RITA R. COLWELL, University of Maryland JOHN EDMOND, Massachusetts Institute of Technology ROBERT M. GARRELS, University of South Florida WILLIAM W. HAY, University of Colorado DENNIS HAYES, Lamont-Doherty Geological Observatory JOHN IMBRIE, Brown University PETER JUMARS, University of Washington MARCUS G. LANGSETH, Lamont-Doherty Geological Observatory KENNETH MACDONALD, University of California, Santa Barbara FRANK MILLERO, University of Miami MICHAEL MULLIN, Scripps Institution of Oceanography WORTH D. NOWLIN, JR., Texas A&M University CHARLES OFFICER, Dartmouth College WILLIAM G. PEARCY, Oregon State University WILLIAM M. SACKERS, University of South Florida FRED N. SPIESS, Scripps Institution of Oceanography KARL TUREKIAN, Yale University PETER VAIL, Exxon Production Research Company WARREN WOOSTER, University of Washington (Chairman 1978-1981) RICHARD C. VETTER, Executive Secretary JAN VORHEES, Consultant DORIS TAYLOR, Administrative Assistant ...

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Board on Ocean Science and Policy G ROSS HEATH, University of Washington, Chairman D. JAMES BAKER, JR., Joint Oceanographic Institutions, Inc. ALAN BERMAN, University of Miami GARRY D. BREWER, Yale University JUDITH M. CAPUZO, Woods Hole Oceanographic Institution PAUL M. EYE, Woods Hole Oceanographic Institution RICHARD H. GAMMON, National Oceanic and Atmospheric Administration EDWARD D. GOLDBERG, Scripps Institution of Oceanography JUDITH T. KILDOW, Massachusetts Institute of Technology JAMES J. McCARTHY, Harvard University H. WILLIAM MENARD, JR., Scripps Institution of Oceanography C. BARRY RALEIGH, Lamont-Doherty Geological Observatory ROGER REVELLE, Scripps Institution of Oceanography BRIAN J. ROTHSCHILD, University of Maryland JOHN H. STEELE, Woods Hole Oceanographic Institution CARL I. WUNSCH, Massachusetts Institute of Technology NANCY G. MAYNARD, Stay Director KAROL McCLELLAND, Administrative Assistant ;v

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Commission on Physical Sciences, Mathematics, and Resources HERBERT FRIEDMAN, National Research Council, Chairman THOMAS BARROW, Standard Oil Company ELKAN R. BLOUT, Harvard Medical School WILLIAM BROWDER, Princeton University BERNARD F. BURKE, Massachusetts Institute of Technology GEORGE F. CARRIER, Harvard University HERMAN CHERNOFF, Massachusetts Institute of Technology CHARLES L. DRAKE, Dartmouth College MILDRED S. DRESSELHAUS, Massachusetts Institute of Technology JOSEPH L. FISHER, Office of the Governor, Commonwealth of Virginia JAMES C. FLETCHER, University of Pittsburgh WILLIAM A. FOWLER, California Institute of Technology GERHART FRIEDLANDER, Brookhaven National Laboratory EDWARD A. FRIEMAN, Science Applications, Inc. EDWARD D. GOLDBERG, Scripps Institution of Oceanography MARY L. GOOD, UOP, Inc. THOMAS F. MALONE, Saint Joseph College CHARLES J. MANKIN, Oklahoma Geological Survey WALTER H. MUNK, University of California, San Diego GEORGE E. PAKE, Xerox Research Center ROBERT E. SIEVERS, University of Colorado HOWARD E. SIMMONS, JR., E.I. du Pont de Nemours & Co., Inc. ISADORE M. SINGER, Massachusetts Institute of Technology JOHN D. SPENGLER, Harvard School of Public Health HASTEN S. YODER, JR., Carnegie Institution of Washington RAPHAEL G. KASPER, Executive Director LAWRENCE E. McCRAY, Associate Executive Director v

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Study Contributors Steering Committee for the Petroleum in the Marine Environment Update GORDON A. RILEY, Bedford Institute of Oceanography, Canada (Retired), Cochairman WILLIAM M. SACKERS, University of South Flonda, Cochairman RITA R. COLWELL, University of Maryland JOHN W. FARRINGTON, Woods Hole Oceanographic Institution C. BRUCE KOONS, Exxon Production Research Company JOHN H. VANDERMEULEN, Bedford Institute of Oceanography, Canada Workshop and Section Area Chairmen Inputs, C. BRUCE KOONS Methods, R1TA R. COLWELL and JOHN W. FARRINGTON Microbial Studies, G. D. FLOODGATE Fates, WILLIAM M. SACKETI and GORDON A. RILEY Biological Processes, RICHARD F. LEE Effects, JOHN H. VANOERMEULEN Processes, CARL SINDERMAN Food Chain, DONALD W. WESTLAKE Ecosystems, Seeps and Spill Case Histories, Plankton, GORDON A. RILEY and JOHN W. FARRINGTON Benthos, DONALD F. BOESCH Workshop Participants Thomas Albert, The North Slope Borough R. C. Allred, Conoco, Inc. *Jack W. Anderson, Battelle Pacific Northwest Karl Banse, University of Washington *Richard Bartha, Rutgers University *Wayne Bell, Hamilton College *William L. Berry, Shell Oil Company Norman J. Blake, University of South Flonda *Paul Boehm, Energy Resources Company *Donald F. Boesch, Louisiana Universities Manne Consortium *James M. Brooks, Texas A&M University R. G. B. Brown, Canadian Wildlife Service *James N. Butler, Harvard University John Calder, NOAA Office of Marine Pollution *Contributed background paper. V1

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G. P. Canevari, Exxon Research and Engineering Company Judith M. Capuzzo, Woods Hole Oceanographic Institution D. W. Chamberlain, Atlantic Richfield Company *R. B. Clark, The University Newcastle-upon-Tyne, England *Robert C. Clark, Jr., NOAA National Marine Fisheries Service Rita R. Colwell, University of Maryland Bruce C. Coull, University of South Carolina Elmer Danenberger, U.S. Geological Survey *Robert A. Duce, University of Rhode Island *F. Rainer Englehardt, Northern Environmental Protection, Canada John W. Farrington, Woods Hole Oceanographic Institution G. D. Floodgate, University College of North Wales H. I. Fuller, Rookery Farm, United Kingdom *Robert B. Gagosian, Woods Hole Oceanographic Institution William D. Garrett, Naval Research Laboratory Richard A. Geyer, Texas A&bl University *Edward-St Gilfillan, Bowdoin College Jack R. Gould, American Petroleum Institute Otto Grahl-Nielson, University of Bergen, Norway Judith Grassle, Woods Hole Oceanographic Institution William O. Gray, Exxon Corporation George Harvey, NOAA, Atlantic Marine Laboratory *Carl Hershner, Virginia Institute of Marine Science *Robert W. Howarth, The Ecosystems Center Thomas Hruby, Massachusetts Audubon Society Walter Japp, Florida Department of Natural Resources James Kittredge, University of Southern California C. Bruce Koons, Exxon Production Research Company *Keith Kvenvolden, U.S. Geological Survey Paul LaRock, Florida State University *John Laseter, University of New Orleans *Richard F. Lee, Skidaway Institute of Oceanography Olof Linden, IVL, Studsvik, Sweden *Arlene Crosby Longwell, NOAA National Marine Fisheries Service Yossi Loya, Tel Aviv University, Israel *Donald MacKay, University of Toronto *Donald C. Malins, NOAA National Marine Fisheries Service James P. Marum, Mobil Oil Corporation Leo T. McCarthy, U.S. Environmental Protection Agency Richard Y. Morita, Oregon State University *Jerry M. Neff, Battelle New England *Bon Olla, NOAA National Manne Fisheries Service *Candace Oviatt, University of Rhode Island *E. H. Owens, Woodward-Clyde Consultants *Jan~es R. Payne, Science Applications, Inc. David Peakall, Canadian Wildlife Service *Errnan A. Pearson, University of California at Berkeley (Retired) William Pequegnat, College Station, Texas *Jon A. Percy, Arctic Biological Station Fred Piltz, U.S. Department of the Interior *James G. Quinn, University of Rhode Island *James P. Ray, Shell Oil Company *Stanley Rice, NOAA National Marine Fisheries Service Gordon A. Riley, Bedford Institute of Oceanography, Canada (Retired) *Cal W. Ross, Mobil Oil Canada, Ltd. William M. Sackett, University of South Florida Alain Saliot, Universite PieITe et Marie Curie, France *Y. S. Sasamura, International Maritime Organization, England Ted Sauer, Exxon Production Research Company *Contributed background paper. vii

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David G. Shaw, University of Alaska Carl Sinderrnan, NOAA National Marine Fisheries Service June Lindstedt-Siva, Atlantic Richfield Company *Woollcott K. Smith, Woods Hole Oceanographic Institution Norman B. Snow, Petro Canada *Robert B. Spies, University of California John H. Steele, Woods Hole Oceanographic Institution *John J. Stegeman, Woods Hole Oceanographic Institution Dale Straughan, University of Southern California *John M. Teal, Woods Hole Oceanographic . . Institution Howard Teas, University of Miami Sunniva Lonning Vader, University of Tromso, Norway *Chase Van Baalen, University of Texas John H. Vandermeulen, Bedford Institute of Oceanography, Canada Edward S. Van Vleet, University of South Florida *Gabriel Vargo, University of South Florida *Sandra Vargo, Florida Institute of Oceanography Richard C. Vetter, National Research Council Jan Vorhees, University of South Florida *John D. Walker, U.S. Environmental Protection Agency Neill Weaver, American Petroleum Institute *Peter G. Wells, University of Toronto, Canada *D. W. S. Westlake, University of Alberta, Canada R. B. Wheeler, Exxon Production Research Company Mary Wolff, City University of New York *Oliver Zafiriou, Woods Hole Oceanographic Institution *Contributed background paper. viii

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Preface The 1975 National Research Council (NRC) report, Petroleum in the Marine Environment, has proven to be an extremely important document. It has been used as a primary source by individuals and groups ranging from scientific investigators to concerned laymen. However, in mid- 1980 it became clear that an update of the 1975 report was necessary. Much of the published material used as a basis for the earlier report predates a workshop held in 1973 that provided most of the background for the 1975 report. Since then, significant new data and information have been published. Thus, the U. S. Coast Guard requested that the Ocean Sciences Board (OSB) (now the Board on Ocean Science and Policy) undertake a new examination of this subject. The OSB appointed a steering committee consisting of cochairmen Gordon A. Riley, Halifax, Nova Scotia, and William M. Sackett, University of South Florida, along with Rita R. Colwell, University of Maryland; John W. Farrington, Woods Hole Oceanographic Institution; C. Bruce Koons, Exxon Production Research Company; and John H. Vandermeulen, Bedford Institute of Oceanography. Later, the National Oceanic and Atmospheric Administration, the Environmental Protection Agency, the Bureau of Land Management (now the Minerals Management Service), Mobil, Exxon, and the Andrew W. Mellon Foundation joined the U.S. Coast Guard in providing financial support for the project. The steering committee took the following major steps. 1. A public meeting was held on November 13, 1980, at which representatives from oil industry, university, government, and environmental groups were invited to make presentations on important topics for consideration by the steering committee. 2. In February 1981, 46 expert contributors were invited to prepare summary papers on all aspects of petroleum in the oceans. These were reviewed and commented on by other experts selected by the . . steering committee. 3. An international workshop was held November 9-13, 1981, where contributors, reviewers, and other invited scientists came together to discuss the main issues brought out from the previous two steps and to make recommendations concerning future research needs. Approximately 90 of the participants came from U.S. university, governmental, and industrial organizations. Another 22 came from Canada, the United Kingdom, France, Gennany, Norway, Israel, and Sweden, providing a strong expert background and a wide range of institutional and foreign governmental expertise to this new report. 4. In February 1982 the steering committee began the task of preparing the new report, based on the input, ideas, and comments obtained by the previous steps. The writing process involved several review steps. Drafts from these iterations were carefully reviewed at several meetings of the entire steering committee. The review process was completed in November 1984. IX

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Contents INTRODUCTION EXECUTIVE SUMMARY Overview, 3 General Advances: 1973-1983, 4 Findings and Recommendations, 6 Summary and Conclusions, 15 1. CHEMICAL COMPOSITION OF PETROLEUM HYDROCARBON SOURCES Introduction, 17 Crude Oils, 17 Refined Products, 23 Oil Seeps and Ancient Sediments, 25 Biogenic Hydrocarbons, 26 Diagenetic Sources, 28 Combustion Sources and Comparison to Petroleum, 28 Other Sources, 29 Diagnosing Sources of Hydrocarbons, 29 Biogenic Sources, 31; Characteristics of Undegraded Petroleum, 31; Characteristics of Petroleum Altered by Physical, Chemical, and Biological Processes, 32; Characteristics of Combustion-Related Hydrocarbons, 36 References, 38 2. ENPUTS ....................................................... Introduction, 43 Natural Sources, 43 Natural Seeps, 45; Geological Implications of Seepage Rates, 48; Erosional Inputs of Petroleum, 49 Offshore Production, 50 Operational (Produced Water) Discharges, 51; Minor Spills, 52; Major Spills, 55 Manne Transportation, 56 Operational Discharges, 58 Crude Oil, 58; Product Oil, 61 17 43 Xl

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Dry-docking, 62 Marine Terminals Including Bunker Operations, 62 Bilge and Fuel Oil, 63 Machine Space Bilges, 63; Fuel Oil Sludge, 64; Oily Ballast From Fuel Oil Tanks, 64 Accidental Spillages, 65 Tanker Accidents, 65; Nontanker Accidents, 65 Atmosphere, 66 Coastal, Municipal, and Industrial Wastes and Runoff, 72 Municipal Wastewaters, 72; Nonrefinery Industrial Wastes, 74; Industrial Wastes From Refineries, 75, Urban Runoff, 76; River Discharges, 78 Ocean Dumping, 78 Geographical Distribution of Inputs, 79 Summary and Recommendations, 81 References, 83 3. CHEMICAL AND BIOLOGICAL METHODS 89 Introduction, 89 General Strategies of Study Design, 89; Sampling Procedures and Equipment, 91; Statistical Design of Analytic Procedures in the Laboratory, 91; Presenting Results From Complex Oil Pollution Studies, 92; Designing Ecological Experiments to Study the Effects of Pollutants, 92; An Oil Spill Survey Design, 93; Summary, 93 Part A: Chemical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ~ . . Introduction, 94 Sampling and Sample Preservation, 95 Sediments, 96; Sediment Traps, 96; Marine Organisms, 97; Seawater, 97; Sampling for Low-Molecular-Weight Hydrocarbons, 98; Sample Preservation, 98 Spilled Oil Characterizations, 99 Sample Collection and Preservation, 99; Analytical Methods, 100 Measurements and Detailed Analysis of Environmental Samples, 102 General, 102; Extraction of Organic Matter (High Molecular Weight, Cal+) Hydrocarbons, 104; Sample Cleanup and Fractionation, 107; Analytical Methods for Cal + Hydrocarbons (Nonvolatiles), 110; Low-Molecular-Weight Hydrocarbons: Analytical Methods, 122 Petroleum Hydrocarbon Intercalibration/Intercomparison Programs, 123 Remote Detection and Measurement of Oil Spills, 128 Monitoring for Petroleum Hydrocarbons, 131 Conclusions and Recommendations, 133 Conclusions, 133; Recommendations, 133 Pad ~ B'alo~ion1 Math Introduction, 135 94 .._, `,^~..,~ .... . . . . . ... .. .... .. . . .. . . . .. . . . .. . . . . .. . 1 35 Physiological, Behavioral, Population, and Ecosystem Effects, 135; Problems of Exposure, Type of Oil, Weathering, and Exposure Medium, 136 Methods for Assessing Toxicity of Petroleum to Marine Organisms, 137 Acute Lethal Toxicity Bioassay, 137; Chronic and Sublethal Effects Studies, 138; Field Studies, 140; Selection of Test Organisms, 140; Preparation of Oil-Water Solutions, 141 - X11

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Bacteria, Yeasts, and Filamentous Fungi, 153 Methods for Estimating Microbial Numbers and Biomass, 153; Methods for Estimating Metabolic Effects of Oil on Microorganisms, 154; Methods for Obtaining Indirect and Direct Measurements of Oil Degradation, 155 Plankton, 156 Phytoplankton, 157; Zooplankton, 161 Accumulation and Modification of Petroleum by Macroorganisms, 164 Field Exposure Methods, 164; Laboratory Exposure Methods, 169 Communities. 180 Sampling Methods, 180; Analysis and Interpretation of Data, 183; Experimental Approaches Beyond the Laboratory, 186 Fish, Seabirds, and Mammals, 187 Fish, 187; Seabirds, 189; Marine Mammals, 192 Cytogenic and Mutagenic Methods, 195 Chromosomal Aberrations, 195; Mutagenesis Assays, 201; Applicability to Petroleum Studies, 202 Ecosystems, 203 Recommendations, 204 References, 206 4. FATES ....................................................... Introduction, 270 Physical and Chemical Fates, 271 Physical and Chemical Characteristics of Petroleum, 271; Processes, 273; Summary and Recommendations, 289 Biological Fates, 290 Introduction, 290; Microbial Biodegradation, 291; Phytoplankton and Marine Algae, 296; Invertebrates and Vertebrates, 297; Factors Influencing Petroleum Biodegradation Rates, 303; Rates of Petroleum Biodegradation in the Marine Environment, 306; Conclusions and Recommendations, 316 Amounts of Hydrocarbons in the Marine Environment, 316 Introduction, 316; Dissolved Petroleum Hydrocarbons, 317; Summary and Recommendations, 335 References, 335 5. EFFECTS ..................................................... Introduction, 369 Toxicity, 372; Laboratory Versus Field Studies, 375; Factors Affecting Impact of Oil, 375; Oil Metabolites and Photochemical Reaction Products, 378; Remedial Measures, 379; Indirect Effects, 383 Effects on Biological Processes, 383 Developmental Problems, 383; Pathological Consequences, 392; Growth and Metabolism, 394; Behavior, 398 Effects on the Marine Food Web, 401 Food Web Microbes, 401; Effects on Marine Plankton, 403; Macrophytes Intertidal and Subtidal, 409; Benthic and Intertidal Invertebrates, 412; Fish, 417; Marine Mammals, 424; Birds, 430 -- Xlll ~7^ 369

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Effects on Communities and Ecosystems, 436 Wetlands, Marshes, and the Intertidal Zone, 437; Coastal and Offshore Waters and Sediments, 440 Special Problem Areas, 449 Tropical Regions, 449; Polar Environments, 458 Effects of Natural Seeps, 468 Seep Studies, 468; Sublethal Effects and Adaptation, 471 Human Heals, 472 Toxicity of Hydrocarbons to Humans Acute Exposures, 472; Carcinogenic Potential in Humans, 477 Summary, 482 Impact of Petroleum, 483; Impact on Processes and Organisms, 484; Impact on Communities, 487; Polar and Tropical Regions, 488; Impact on Human Health, 489; Petroleum and Other Chemical Contaminants, 489 Conclusion, 489 Research Recommendations, 490 References, 491 APPENDIX A Impact of Some Major Spills (Spill Case Histories' Introduction, 549 An Inshore Spill: The Barge Florida, 550 An Open Bay Spill: The Arrow, 553 An Open Ocean Spill With Offshore Winds: The Argo Merchant, 557 A Near-Shore Spill With Onshore Wind: The Amoco Cadiz, 561 An Underwater Blowout: Ixtoc I, 567 An Onshore Tropical Spill: The Zoe Colocotroni, 572 Summary and Discussion, 573 References, 576 APPENDIX B Abbreviated Terms APPENDIX C Public Meeting Participants, November 13, 1980 Washington, D.C. , --------------- INDEX 549 583 xiv 586 587

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List of Figures 1-la Chemical structure of petroleum hydrocarbons, 24 1-lb Chemical structure of petroleum hydrocarbons, 25 1-lc Nonhydrocarbon petroleum constituents: NSO compounds, 26 Boiling point range of fractions of crude petroleum, 27 1-3 Relative abundance of parent aromatic compound and alkyl substituents as influenced by temperature of fo~ation, 29 1-4 PAH alkyl homolog distributions for sewage sludge and dredge spoils, 30 1-5 Glass capillary gas chromatograms of time series for fresh petroleum and petroleum subjected to alteration by natural processes in sediments, 34 1-6 Gas chromatographic mass spectrometry selected ion searches for pentacyclic triterpanes (hopanes) in Amoco Cadiz reference oil and November 1978 weathered oil in sediments, 37 2-l International marine transportation routes for petroleum, 44 2-2 Location of reported marine seeps, 47 3-l Analytical options for analysis of petroleum compounds in sediment, tissue, particulate matter, and water, 103 Representative petroleum hydrocarbon separation techniques, 108 Hierarchical scheme for analyses of petroleum hydrocarbon in environmental samples, l l l 3-4 UV/F scan modes, 114 3-5 Representative synchronous fluorescence spectra of water samples collected near the Ixtoc I blowout, 1 15 3-6 Solubilizer systems for exposing organisms to water-soluble fractions of crude oil, 148 3-7 3-8 Fuel oil dispersion and bioassay apparatus, 150 Plots of coefficients of variation for species populations in communities of macrobenthos near West Falmouth, Massachusetts, 185 4-1 Schematic of physical, chemical, and biological processes, 271 4-2 Surface concentration of spill, 274 4-3 Photooxidation of benzota~pyrene, 281 4-4 Degradative pathways of petroleum hydrocarbons, 294 xv

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4-5 Proposed pathways for the metabolism of napthalene by Oscillatoria sp., strain JCM, 297 4-6 Diagram of cytochrome P450-dependent metabolism of benzofa~pyrene, 308 5-1 Acute toxicity of some aromatic hydrocarbons for selected marine macroinvertebrates and fish, 373 5-2 Effects of oiling on fine structure of surf smelt embryo retinas, 374 5-3 Schematic diagram of the offshore "mesocosm" study at Loch Ewe, Scotland, and changes in zooplankton populations observed with the introduction of petroleum, 410 5-4 Toxicity of No. 2 fuel oil to life-cycle stages of selected marine shrimp and polychaetes, 413 5-5 Subtidal invertebrates such as sea urchins and razor clams proved to be highly vulnerable to the oil spilled from the Amoco Cadiz tanker, off the coast of France, 1978, 415 5-6 Oiled and unoiled harbor seal pups seen on Sable Island, Nova Scotia, Canada, in June 1979, 426 5-7 Schema of ecological succession of benthic infauna species after oiling of intertidal sediments (a three-part figure), 441 5-8 Oil pollution at coral nature reserve of Eilat, Red Sea, 450 5-9 Effects of oil on a mangrove forest, 457 5-10 Radioautogram of metabolites formed from (1-~4C) naphthalene by ice-edge diatoms isolated from the Bering Sea, 467 5-1 1 One potential route of oil contact with man is through eating of oiled seafood, as by this North Brittany coastal resident digging for clams in sediments oiled by the Amoco Cadiz tanker spill in 1978, 473 A-1 Faunal discrepancy indices at various stations in Buzzards Bay, Massachusetts, following the Florida spill, 554 A-2 Mean wind vectors over Chedabucto Bay, February 3-12, 1970, 555 A-3 Geographical extent of shoreline contamination in Chedabucto Bay, February 1970, immediately following Arrow breakup, 556 A-4 Erosion pattern of stranded Arrow Bunker C fuel oil on Chedabucto Bay shorelines, 1970-1976, 557 A-5 Summary of stranded Bunker C fuel oil reentry pattern into marine environment by oil stranded on low energy gravel-cobble beach, 558 A-6 Horizontal dispersion of oil spilled from the Argo Merchant, December 17, 20, and 23, 1977, 559 A-7 Horizontal extent of oil movement from the Amoco Cadiz spill, 562 A-8 Pattern of the persistence of Amoco Cadiz oil in coastal waters and sediments of Brittany, France, April 1978 to April 1981, 563 A-9 Location of the Ixtoc I blowout and the initial path of the slick movements, 568 A-10 Schematic diagram of the Ixtoc I blowout, 569 xvi

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List of Tables 1-la 1-lb 1-lc 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 2-9 2-10 2-11 2-12 2-13 2-14 2-15 2-16 2-17 2-18 2-19 2-20 2-21 2-22 3-1 3-2 3-3 3-4 3-5 3-6 Physical characteristics and chemical properties of several crude oils, l9 Physical characteristics and chemical properties of two refined products, 21 Examples of individual polynuclear aromatic hydrocarbon concentrations in petroleum, 23 Petroleum transport at sea, 45 Petroleum resource estimates, 48 Maximum lifetimes (million years) of world oil deposits, 49 Offshore petroleum production, 1979, 51 Offshore produced water effluent limitations, 53 Oil to the marine environment from offshore produced water discharges, 54 Minor oil spills, Gulf of Mexico outer continental shelf, 1972-1978, 55 Oil to the marine environment from minor spills, 56 Major spills, Gulf of Mexico outer continental shelf, 1971-1978, 57 Oil to the marine environment from major spills, 58 Results of LOT operation efficiency tests, 60 Annual quantity of oil spills due to tanker accidents, 65 Summary of transportation losses (mta), 66 Particulate n-alkane concentrations in the marine atmosphere (ngIm3 STP), 69 Vapor phase n-alkanes in the marine atmosphere (ng/m3 STP), 70 Summary of atmospheric inputs of n-alkanes to the ocean (mta), 71 NRC estimates of hydrocarbons to world ocean, from municipal and industrial wastes and runoff (mta), 73 Global discharge of hydrocarbons in municipal wastewaters, 75 Estimated global discharge of petroleum hydrocarbons into refinery wastewaters, 77 Selected urban runoff studies, 78 Per capita estimates of PHC contributions in urban runoff, 79 Input of petroleum hydrocarbons into the marine environment (mta), 82 Matrix of oil concentrations in sediments and correlations with benthic organism biomass, 91 Summary of interlaboratory intercalibration exercises, 1976-1981, 125 Oil spill detection by remote sensing; sensors and spectral regions, 130 Concentrations of C~2-C24 e-paraffins and aromatic hydrocarbons in reference oils and the 10% water-soluble fractions (WSFs) prepared from them, 144 Compositional comparison of reference oils on a basis of those hydrocarbons measured, 145 Experimental field methods for exposing marine macroorganisms to petroleum contaminants, 166 xvii

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3-7 4-1 4-2 4-3 44 4-5 4-6 4-7 4-8 4-9 4-10 4-11 5-1 5-2 5-3 5-4 5-5 5-6 5-7 5-8 5-9 5-10 5-11 5-12 5-13 5-14 5-15 5-16 5-17 5-18 Laboratory methods for exposing marine macroorganisms to hydrocarbon contaminants, 170 Henry's law constants for selected hydrocarbons, 273 Petroleum photooxidation summary, 282 Uptake and loss of petroleum hydrocarbons in bivalves under laboratory or microcosm conditions, 300 Amounts of petroleum hydrocarbon in bivalves from contaminated areas, 301 Estimates under temperate conditions of hydrocarbon biodegradation rates, 307 Microsomal benzofa~pyrene metabolism in some marine animals, 310 Comparison of metabolizes of naphthalene in liver, muscle, and bile of starry flounder (Platichthys stella ask, 312 Induction by hepatic ben%ofa~pyrene hydroxylase in marine fish by aromatic hydrocarbons, 313 Tar densities on the world oceans, 324 Hydrocarbons in marine sediments, 327 Petroleum hydrocarbons in bottom-dwelling marine organisms, 332 Emphasis of oil-pollution-related study reports for the temperate and northern marine environment between 1967 and 1977, 370 Acute lethal toxicity of some oil spill dispersants to marine organisms a selection of current data, 382 Mutagenicity of petroleum and its components, 386 Summary of gill morphology in rainbow trout (Salmo gairdneri) following 7 days of oil treatment, comparing different modes of exposure, 393 Lethality (median lethal concentrations) of physically dispersed and water-soluble fractions of various oils to marine zooplankton, 406 Experimental conditions of three field enclosure systems or mesocosms, 408 Effects of oil on eggs and embryos of marine fish, 419 Summary of effects of oil on marine fish larvae, 420 Relationship between amount of oil spilled in an incident and number of dead birds found, 433 Summary of known long term biological effects of some major marine oil spills, 438 Summary of effects of oil spills on coral reefs, 451 Comparison of the impact of some oil spills on mangroves, 454 Summary of studies on the sublethal effects of petroleum hydrocarbons on polar marine organisms, 459 Suggested inhalation exposure standards in humans for a variety of petroleum hydrocarbons, 475 Benzofalpyrene content of selected petroleum products, 478 PAH levels in foodstuffs, 480 Estimated human exposure to benzofa~pyrene through respiratory and gastrointestinal intake, 481 Effects of low concentrations (less than 1 ppm) of petroleum hydrocarbons on marine organisms in laboratory and mesocosm studies, 485 Estimates of the distribution of oil spilled from the tankers Arrow, Zoe Colocotroni, and Amoco Cadiz, 575 xviii

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OIL IN TO INPUTS, FATES, AND EFFECTS SEA

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