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The Chemistry and Formation of Water-In-Oil Emulsions and Tar Balls from the Release of Petroleum in the Marine Environment

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The Chemistry and Formation of Water-In-Oil Emulsions and Tar Balls from the Release of Petroleum in the Marine Environment _—. —.— — .——. —- —.. ..— — THE CHEMISTRY AND FORMATION OF WATER-IN-OIL EMULSIONS AND TAR BALLS FROM THE RELEASE OF PETROLEUM IN THE MARINE ENVIRONMENT James R. Payne DivisiorI of Environmental Chemistry and Geochemistry Science Applications, Inc. La Jolla, California 92038 ——— . _____ .— .. —- —— ——-— —- PREFACE This manuscript is based on a review n~epared as a contribution to the NAS Petroleum in the Marine Environment/Update Workshop held November 9-13, 1981, and it may or may not reflect the concensus of the workshop par- ticipants or the National Academy of Sciences. A summary publication of those proceedings is anticipated in 1983; however, there are currently no plans to publish” the background papers per se. Thus, this text is the direct result of the author’s desire to make its contents available to a wider audience of interested parties in the scientific and industrial community. I am grateful to a number of my col?egues and peers who have encouraged me over the several months which have elapsed since the NAS review to publish this material in its present form. The original draft of the manuscript was reviewed by Dr. James N. Butler of Harvard University and Mr. Gerard P. Canevari of Exxon Research and Engineering Company. Their comments and suggestions have been incorporated throughout the text where appropriate; however, this author must assume respon- sibility for any omissions or errors :ntroduced in reviewing the rather extensive amount of literature published on the subject. I am deeply indebted to G. Daniel McNabb, James Lambach, Robert Redding, and William Paplawsky for the analyses of the samples from Kasitsna Bay, Alaska, discussed in the book. I would also like to thank Cheryl Fish, Suzanne Goldman, Mabel O’Byrne, Randee Luedecke and Nancy Burnett for their able assistance in the preparation of this manuscript, its tables and figures. James Lambach and Randolph E. Jordan were also instrumental in obtaining much of the liter~’ture cited and in compiling the various references for the Bibli- ography. Oil weathering research programs related to the subject of this re- view have been funded (wholly or in part} by NOAA/Office of Marine Pollution Assessment, Contract No. NA80RAC 00013, Cooperative Research in Investigating . ..— —— —. .— the IXTOC I Blowout; NWL4/Outer Continental Shelf Environmental Assessment Program, Contract No. 03-7-002-35213, Preparation of a Literature Review on the Fate and Weathering of Petroleum Spills in the Marine Environment; and by the Bureau of Land Management through interagency agreement with the National Oceanic and Atmospheric Administration, as part of the Outer Continental Shelf Environmental Assessment Program, Contract No. NA80RAC 00(318, Mliltivariate Analysis of Oil Weathering in the Marine Environment - Sub Arctic. James R. Payne, Ph.D. April 9, 1982 La Jolla, California ii .-— TABLE OF CONTENTS TITLE PAGE INTRODUCTION . 1 LABORATORY STUDIES OF FORM4TION AND STABILITY OF WATER-IN-OIL EMULSIONS. 4 Background. ~ Specific Studies. 6 Identification of Emulsifying Agents Responsible for Mousse Formation. 20 Physical and Behavioral Properti-es of Mater-in-oil Enwlsions . ● . 24 Breaking and Integration of Laboratory Mousse with Dispersants. ✎ . 34 Bacterial Utilization of Laboratory Generated Mousse . ✎ . 40 SELECTED CASE HISTORIES OF THE KIRE DETAILED CHEMISTRY STUDIES OF MOUSSE BEHAVIOR AND LONG TERM FATE IN NEAR- COASTAL AND OPEN OCEAN OIL SPILLS/BLOMOUTS. 41 TorreyCanyon. 41 Tanker Arrow. ● . 42 Metula. ✎ . 46 Ekofisk Bravo Blowout . ● . ✎ . 47 US/NS Potomac in Melville Bay, Greenland. ✎ . ✎ . 51 Amoco Cadiz ..,..... ✎ . ✎ . 53 IXTOC I Blowout, Bay of Campeche, Gulf of Mexico....,.. ● ✎ . ✎ . 59 Background . ● ✎ . ✎ . 59 Observations at the !dellhead . ✎ ✎ . ✎ . 65 Subsurface Transport and Weathering of IXTOCOil . ✎ ✎ . ✎ . 69 Observations of Micro-Scale Mousse Formation . ✎ ✎ . ✎ . 72 Fate of Stranded IXTOC Mousse Along the Southeast Texas Coastline. ✎ ✎ . ✎ . 80 Burmah Agate. ✎ ✎ . ✌ . 82 Open Ocean Field Tests of Spilled Petroleums . ✎ ✎ . ✎ ● . 83 Conclusions. ✎ ✎ . ✎ ✎ . 87 TAR BALL FORF!ATION ANO DISTRIBUTION . ✎ ✎ . ✎ ✎ . 89 Chemical Composition of Tar Balls . ✎ ✎ . ✎ ✎ . “91 . 111 ———— .— . ——- .— — TABLE OF CONTENTS (CONTINUED) TITLE PAGE Sources of Pelagic Tar . 96 Fate of Beached or Stranded Tar Balls . 101 DEVELOPMENT OF ALGORITHMS AND COMPUTER PROGRAMS TO SIMULATE THE FORMATION OF WATER-IN-OIL EMULSIONS . 104 SUMMARY . 120 Laboratory Studies . , , . ● . 120 Physical Properties of Water-in-Oil Emulsions . ● ✎ . 121 Treatment of Mousse with I)ispersants . , . ✎ ✎ . 122 Case Histories of Real Spill Events . ● ✎ ✎ . 123 Tar Ball Distributions and Chemistry . ✎ ✎ ✎ . 125 Mathematical and Ccmputer Modeling of Mousse Behavior. 127 ACKNOWLEDGEMENTS . 128 31 BLIOGRAPHY . ..0...... 729 <., d iv . ..— .— - — -— LIST 0FTABLE5 TABLE TITLE PAGE 1 Mousse Fornntion Experinients using a Variety of Fresh and Artificially Weathered (Topped) Crude Oils in Laboratory, Outdoor Test Tank, and Field Experiinental Spills. 7 2 Other 01s Which Have Demonstrated Water-in-Oil Emulsion Tendency, . 10 3 Time-series water column concentrations (YQ1 of dissolved dispersed hydrocarbons from fresh Prudhoe Bay crude oil and mousse weathering on flow-through seawater enclosures (turbu? en~ regi,me) at Kasitsna Bay, Alaska. (Water temp- erature 6 C, air temperature 6 - 13°C), Concentrations determined by capillary temperature-programmed FID gas chromatography. , . 32 4 Inhibition of Stable Mousse Formation by the Addition of Chemical Dispersants. 35 5 Chemical Studies of Oil/Mousse Behavior in Major Oceanic Spills and Blowouts. 41a 6 Selected Component Ratios for the Dissected Mousse Sample Beached at Laguna Madre (Station RIX 23) . 79 7 Summary of 1971-1980 Citations of Tar Ball Distributions and Concentrations on the World Oceans . , . 90 8 Summry of 1971-1976 Stranded Tar Ball Distributions and Concentrations on Beach Surfaces . 102 . ——— LIST OF FIGURES * . FIGURE TITLE PAGE 1 Flame Ionization Detector - Temperature Programmed Gas Chroma- tograpiiic Analysis of Tenax-Trapped Volatile Compounds Lost From Fresh Prudhoe 8ay Crude Oil After I hour of Weathering (I!ith Turbulence) on Seawater. 25 2 Flame Ionization Detector - Temperature Programmed Gas Chroma- tographic Analysis of Tenax-Trapped Volatile Compounds Lost From Fresh Prudhoe Bay Mousse (80% Water) After 1.5 hours of !Jeathering (With Turbulence) on Seawater . 26 3 Tenax Trap/FID GC Data on Sub-Arctic Volatile Component Loss From Prudhoe Bay Crude Oil and Mousse on Flow-Through Seawater Enclosures in Kasitsna Bay, Alaska . , . 28 4 Computer Generated Plots of Capillary FID-GC Data on Inter- mediate Molecular Weight Components Remaining in Prudhoe Bay Crude Oil and Mousse Weathering Under Sub-Artic Conditions on Flow-Through Seawater Enclosures at Kasitsna Bay, Alaska. 29 !5 Computer Generated Plots of Capillary FID-GC Data on Higher Molecular Weight Components Remaining in Prudhoe Bay Crude Oil and Mousse Weathering Under Sub-Arctic Conditions on Flow Through Seawater Enclosures at Kasitsna Bay Alaska . 30 6 Relative Abundance of Alkyl-Substituted Polynuclear Aromatic Hydrocarbons in IXTOC Crude Oil Collected 1/2 Mile from the Well Head. 76 7 Abundance of N-Alkanes (Relative to nC-20) in Beached Mousse . from Laguna Madre (RIX-23), Mousse Flakes Collected 16-18 Miles from the WfeJl Head (P-23) during the GW Pierce Down- Plume Transect, and IXTOC Crude Collected 1]2 Mile from the Well Head. , 77 8 Mousse/Oil (u/Po) Relative Viscosity Ratio of Six Test Crude Oils as a Function of !iater Content. 106 9 Computer Model - Predicted and Observed Time-Dependent Uptake of Water into Ekofisk oil as a Function of Wind Speed and Sea-State . ,. ,109 ui ——..—. INTRODUCTION The requirements for understanding and being able to predict the formation of . water-in-oil emulsions, sometimes described as “chocolate mausse”, are critical components in our ability to control and mitigate the environmental impacts of petroleum hydrocarbon spills in marine and coastal waters. Stable water-in-oil emulsions or mousse can compound clean-up strate- gies and logistics, as the more viscous mousses can present formidable problems in skimming, pumping and recovery operations. Mousse can take up an inordinate amount of space fn transport and intermediate storage due to the often noted factor of 4 to 5 increase in volume from water incorporation, and in the final stages of disposal certain water-in-oil emulsions may resist more ‘ convenient and conventional disposal mechanisms such as burning. When crude oil and many refined products are released at sea they are immediately subjected to a series of weathering processes including: spread- ing, evaporation and dissolution of selected lower molecular weight compo- nents, dispersion of whole oil droplets into the water column, coalescence of these droplets and return to the surface slick with entrapment of seawater, photo-, microbial- and auto-oxidation, and emulsification and tarball forma- tion. The rates of these comcommitant processes are inextractably linked (and in some cases compete) with one another and are dependent on the type and amount of oil spilled (component concentrations), the environmental conditions (water and air temperature, wind speed, and turbulence regime -- sea state) and man’s own efforts to control or disperse the slick through the application of dispersants (emulsifying agents) and/or adsorbant products to enhance sinking. ( Most crude oils and refined petroleum products have specific gravi-
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