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EPA/600/R-03/072 July 2003 Characteristics of Spilled Oils, Fuels, and Petroleum Products: 1. Composition and Properties of Selected Oils Zhendi Wang, B.P. Hollebone, M. Fingas, B. Fieldhouse, L. Sigouin, M. Landriault, P. Smith, J. Noonan, and G. Thouin Emergencies Science and Technology Division Environmental Technology Centre Environment Canada 335 River Road, Ottawa, Ontario James W. Weaver Project Officer Ecosystems Research Division Athens, Georgia 30605 National Exposure Research Laboratory Office of Research and Development United States Environmental Protection Agency Research Triangle Park, North Carolina 27711 Notice The U.S. Environmental Protection Agency through its Office of Research and Development funded and managed the research described here under contract (1D-5859-NAFX) to Environment Canada. It has been subjected to the Agency’s peer and administrative review and has been approved for publication as an EPA document. Mention of trade names or commercial products does not constitute endorsement or recommendation for use. ii Foreword The National Exposure Research Laboratory’s Ecosystems Research Division (ERD) in Athens, Georgia, conducts research on organic and inorganic chemicals, greenhouse gas biogeochemical cycles, and land use perturbations that create direct and indirect, chemical and non-chemical stresses, exposures, and potential risks to humans and ecosystems. ERD develops, tests, applies and provides technical support for exposure and ecosystem response models used for assessing and managing risks to humans and ecosystems, within a watershed / regional context. The Regulatory Support Branch (RSB) conducts problem-driven and applied research, develops technology tools, and provides technical support to customer Program and Regional Offices, States, Municipalities, and Tribes. Models are distributed and supported via the EPA Center for Exposure Assessment Modeling (CEAM) and through access to Internet tools (www.epa.gov/athens/onsite). At the request of the US EPA Oil Program Center, ERD is developing an oil spill model that focusses on fate and transport of oil components under various response scenarios. Since crude oils and petroleum products are composed of many chemicals that have varying physical properties, data are required to characterize these fluids for use in models. The data presented in this report provide input to compositional models by characterizing oil composition by several approaches, but also by providing physical transport properties at corresponding levels of weathering and temperature. EPA expects these data to be useful both for modeling and to provide a resource for the oil spill response community as a whole. Rosemarie C. Russo, Ph.D. Director Ecosystems Research Division Athens, Georgia iii Abstract Multicomponent composition and corresponding physical properties data of crude oils and petroleum products are needed as input to environmental fate simulations. Complete sets of such data, however, are not available in the literature due to the complexity and expense of making the measurements. Environment Canada has previously developed a database of various physical and chemical properties of crude oils and petroleum products. In this cooperative project, ten “typical” crude oils and refined products in common use or transport were identified for subsequent characterization. Measured oil physical properties include API gravity, density, sulphur content, water content, flash point, pour point, viscosity, surface and interfacial tension, adhesion, the equation for predicting evaporation, emulsion formation, and simulated boiling point distribution. The chemical composition of the oils are quantified for hydrocarbon groups, volatile organic compounds, n-alkane distribution, distribution of alkylated polyaromatic hydrocarbon (PAH) homologues and other EPA priority PAHs, and biomarker concentrations. This project will provide the most complete and comprehensive database for the selected oils to date. The new composition data will be integrated into the existing Environment Canada oil properties database. The results will be made available to the public both on the world wide web and as a database on disc. iv Table of Contents Notice .................................................................... ii Foreword ................................................................ iii Abstract .................................................................. iv 1. Introduction .......................................................... 1 2. List of Definitions ..................................................... 3 3. Methods for Measurement of Physical and Chemical Properties of Selected Oils ..... 10 4. Summary of Quality Assurance and Quality Control (QA/QC) Plan ............... 28 5. Physical Properties and Chemical Composition of Alaska North Slope Crude Oil (2002) .................................................................. 34 6. Physical Properties and Chemical Composition of Alberta Sweet Mixed Blend (ASMB, Reference #5) ................................................................ 46 7. Physical Properties and Chemical Composition of Arabian Light (2000) ............ 58 8. Physical Properties and Chemical Composition of Sockeye (2000) ................ 70 9. Physical Properties and Chemical Composition of South Louisiana (2001) .......... 82 10. Physical Properties and Chemical Composition of West Texas Intermediate (2002) . 94 11. Physical Properties and Chemical Composition of Fuel Oil No. 2/Diesel (2002) ..... 106 12. Physical Properties and Chemical Composition of Fuel Oil No. 5 (2000) .......... 118 13. Physical Properties and Chemical Composition of Heavy Fuel Oil 6303 (2002) ...... 129 14. Physical Properties and Chemical Composition of Orimulsion-400 (2001) ......... 140 15. Trace Metals ....................................................... 148 v 16. References ......................................................... 149 17. Appendices ........................................................ 153 1 Chemical Abstract Service (CAS) Registry Numbers for Selected Analytes ...... 153 2 Oil Chemical Analysis Protocol ....................................... 156 3 GC Chromatograms for Alaska North Slope Crude Oil ...................... 157 4 GC Chromatograms for Alberta Sweet Mixed Blend #5 Crude Oil ............. 170 5 GC Chromatograms for Arabian Light Crude Oil .......................... 182 6 GC Chromatograms for Sockeye Crude Oil .............................. 194 7 GC Chromatograms for South Louisiana Crude Oil ........................ 208 8 GC Chromatograms for West Texas Intermediate Crude Oil .................. 220 9 GC Chromatograms for Fuel Oil Number 2 .............................. 231 10 GC Chromatograms for Fuel Oil Number 5 ............................. 245 11 GC Chromatograms for HFO 6303 ................................... 257 12 GC Chromatograms for Orimulsion-400 ................................ 270 vi 1. Introduction During any oil spill incident, the properties of the spilled oil, including the oil phase composition and oil compositional changes due to weathering, ideally would be known immediately, so that models could be used to predict the environmental impacts of the spill or various treatment alternatives. Unfortunately, the properties routinely measured by oil producers and refiners are not the ones that on-scene commanders need to know most urgently. Oil producers and refiners typically do not know to what extent or at what rate their oils will evaporate; the detailed chemical composition of the oil and its differential compositional changes over time; how these changes affect its behavior and fate in the environment; the viscosity of the oil at ambient temperature as it evaporates; if the oil likely to sink or submerge; if the use of chemical dispersants can enhance its dispersion; if emulsions will form; the hazard to on-site personnel during cleanup; or the oil toxicity to marine or aquatic organisms. Since 1984, the Emergencies Science and Technology Division (ESTD) of Environment Canada has continued to develop a database on various physical-chemical properties of crude oils and petroleum products. This database addresses the properties and behaviors listed in the previous paragraph and can be queried via the internet at www.etcentre.org/spills. Through many years endeavor, the oil properties database now contains information on over 400 oils from all over the world. Environment Canada is the largest single source of data in the oil properties database. The U.S. EPA’s immediate interest in developing a database of properties and compositions is for use in supporting the development of models for application to accidental spills and releases of petroleum hydrocarbons and other multicomponent oils. This multicomponent composition data is not typically available in the literature nor immediately available on an incident-specific basis due to the complexity and expense of making the measurements. Thus the creation of a database containing both physical property and composition data for various conditions of weathering would be useful for emergency response modeling. In this situation the data could be used for simulation of an example oil that would be chosen for its similarity to the spilled oil. This approach recognizes that performing detailed characterization of an oil during an emergency is more than unlikely. It would further be desirable to have access to similar data for planning purposes in advance of spills. Ten representative
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