Petroleum Biodegradation and Oil Spill Bioremediation Karuna K. Arjoon KKA Associates California, Trinidad and James G. Speight CD&W Inc. Laramie, USA p, A SCIENCE PUBLISHERS BOOK A SCIENCE PUBLISHERS BOOK First edition published 2023 by CRC Press 6000 Broken Sound Parkway NW, Suite 300, Boca Raton, FL 33487-2742 and by CRC Press 4 Park Square, Milton Park, Abingdon, Oxon, OX14 4RN © 2023 Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, LLC Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use. The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint. Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, access www.copyright.com or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. For works that are not available on CCC please contact [email protected] Trademark notice: Product or corporate names may be trademarks or registered trademarks and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging‑in‑Publication Data (applied for) ISBN: 978-0-367-48739-3 (hbk) ISBN: 978-1-032-41115-6 (pbk) ISBN: 978-1-003-04263-1 (ebk) DOI: 10.1201/9781003042631 Typeset in Times New Roman by Radiant Productions Preface It is not the purpose of this book to condemn the crude oil refining industry as the bad actor in terms of environmental pollution. In fact, there are many areas of the chemical industry that are responsible for the release of pollutants into the environment. The refining industry is one such industry that has seen inadvertent spillage of unrefined crude oil and crude oil products. The continuing question, since the beginning of the environmental movement in the 1960s, relates to the relative condition of the environment. However, it is the purpose of the book to identify effective clean-up methods for the spills of crude oil and crude oil products (as well as the spills of other chemicals) that is both economically and ecologically suitable is of paramount urgency for continued existence of humanity. Thus far, bioremediation has been gaining momentum as a valuable clean-up method of many environmental hazards over the past three-to-four decades. In this book, other than the terms crude oil and crude oil product, the term oil is often substituted to describe a broad range of hydrocarbon-based chemicals which includes substances that are commonly thought of as oils, such as crude oil and refined petroleum products. Each type of oil has distinct physical and chemical properties. These properties affect the way oil will spread and break down, the hazard it may pose to aquatic and human life, and the likelihood that it will pose a threat to natural and man-made resources. Bioremediation is the use of natural organisms to eliminate many components of crude oil and crude oil products from the environment. The concern is whether or not bioremediation technologies can accelerate this natural process enough to be considered practical, and, if so, whether they might find a niche as replacements for, or adjuncts to, other crude oil-spill response technologies. Crude oil (also called petroleum) is a complex mixture of thousands of different chemical compounds. In addition, the composition of each accumulation of oil is unique, varying in different producing regions and even in different unconnected zones of the same formation. The composition of crude oil also varies with the amount of refining. Significantly, the many constituents of crude oil differ markedly in volatility, solubility, and susceptibility to biodegradation—some constituents are susceptible to microbial biodegraded while others non-biodegradable. Furthermore, the biodegradation of different crude oil constituents occurs simultaneously but at very different rates. This leads to the sequential disappearance of individual components of crude oil over time and, because different species of microbes preferentially attack different compounds, to successional changes in the degrading microbial community. Thus, to evaluate the effectiveness of biodegradation, through the application of bioremediation technologies it is necessary to know the molecular effects of the process starting with the molecular composition of the contaminants. This book introduces the reader to the science and technology of bioremediation—a key process for the removal of crude oil and crude oil based contaminants at spill sites. The contaminants of concern in the molecularly-variable crude oil and crude oil products can be degraded under appropriate conditions. But the success of the process depends on the ability to determine the necessary conditions and establish them in the contaminated environment. iv Petroleum Biodegradation and Oil Spill Bioremediation Although the prime focus of the book is to determine the mechanism, extent, and efficiency of biodegradation processes it is necessary to know the composition of the original crude oil or crude oil product. The laws of science dictate what can or cannot be done with crude oil and crude oil products to insure that biodegradation (hence, bioremediation) processes are effective. The science of the composition of crude oil and crude oil products is at the core of understanding the chemistry of biodegradation and bioremediation processes. Hence, inclusion of crude oil analyses and properties along with crude oil product analyses and properties is a necessary part of this text. It is the purpose of this book to present to the reader an introduction to the science and technology of bioremediation as applied to the spills of crude oil. Bioremediation is a key process that can be applied to the removal of contaminants that arise from the spill of crude oil or crude oil products. The contaminants of concern in the molecularly-variable constituents of crude oil and crude oil products can be degraded under appropriate conditions. However, the success of the bioremediation process depends on the conditions at the spill site and the ability to establish the necessary conditions to decontaminate the site. To accomplish this goal, the book focuses on the various aspects of environmental science and engineering as applied to the crude oil and crude oil products. The initial section (Part I) presents an introduction to crude oil and crude oil products. The second section (Part II) introduces the reader to the nature of oil spills and the concept if bioremediation and biodegradation and presents descriptions of site evaluation, methods for bioremediation, the analytical methods that can be used to determine the extent of the cleanup, and the various cleanup methods, and degradation methods, recommendations for oil spillage prevention, control, and the future of bioremediation. Each chapter includes a copious reference section and the book is further extended and improved by the inclusion of an extensive Glossary. In addition, a basic knowledge of the organic chemistry of the constituents of crude oil and crude oil products is necessary and, for those readers not fully familiar with this area of chemistry, an explanation of the chemistry of crude oil constituents is included for reference (Appendix A). Karuna K. Arjoon, MPhil California, Trinidad and Tobago James G. Speight PhD, DSc, PhD Laramie, Wyoming, USA Contents Preface iii Glossary xiii PART I: Crude Oil and Crude Oil Products 1. Crude Oil Composition and Properties 3 1.1 Types of Crude Oil 7 1.1.1 Conventional Crude Oil 9 1.1.2 Heavy Crude Oil 11 1.1.3 Extra Heavy Crude Oil 12 1.1.4 Tar Sand Bitumen 12 1.2 Crude Oil Composition 15 1.2.1 Elemental Composition 18 1.2.2 Chemical Composition 18 1.2.3 Composition by Volatility 21 1.2.4 Composition by Fractionation 22 1.2.5 Composition by Spectroscopy 23 1.2.5.1 Infrared Spectroscopy 23 1.2.5.2 Nuclear Magnetic Resonance Spectroscopy 24 1.2.5.3 Mass Spectrometry 24 1.2.5.4 Other Techniques 24 1.3 Crude Oil Properties 24 1.3.1 Density and Specific Gravity 28 1.3.2 Elemental Analysis 28 1.3.3 Chromatographic Fractionation 29 1.3.4 Liquefaction and Solidification 30 1.3.5 Metals Content 31 1.3.6 Surface Tension and Interfacial Tension 31 1.3.7 Viscosity 32 1.3.8 Volatility 33 1.4 Summary 34 References 35 2. Crude Oil Products 37 2.1 Refinery Products 40 2.2 Bulk Products 42 2.2.1 Liquefied Petroleum Gas 43 2.2.2 Naphtha, Gasoline, and Solvents 44 vi Petroleum Biodegradation and Oil Spill Bioremediation 2.2.3 Kerosene and Diesel Fuel 48 2.2.4 Fuel Oil 49 2.2.5 Lubricating Oil 51 2.2.6 White Oil, Insulating Oil, Insecticides 52 2.2.7 Grease 54 2.2.8 Wax 54 2.2.9 Asphalt 55 2.2.10 Coke 60 2.3 Petrochemical Products 61 2.4 Occurrence and Uses of Common Hydrocarbon Derivatives 63 2.5 Refinery Waste 67 2.5.1 Acid Sludge 71 2.5.2 Spent Acid 72 2.5.3 Spent Catalyst 73 2.5.4 Spent Caustic 74 2.5.5 Sulfonic Acids 74 2.5.6 Product Blending 75 2.5.7 Waste by Process 76 2.5.7.1 Dewatering and Desalting 78 2.5.7.2 Gas Processing 80 2.5.7.3 Distillation 80 2.5.7.4 Visbreaking and Thermal Cracking 82 2.5.7.5 Coking Processes 82 2.5.7.6 Fluid Catalytic Cracking 83 2.5.7.7 Hydrocracking and Hydrotreating 84 2.5.7.8 Catalytic Reforming 86 2.5.7.9 Alkylation 86 2.5.7.10 Isomerization and Polymerization 87 2.5.7.11 Deasphalting 88 2.5.7.12 Dewaxing 89 2.5.8 Types of Waste 89 2.5.9 Waste Toxicity 96 2.6 Entry into the Environment 96 2.6.1 Storage and Handling of Crude Oil and Crude Oil Products 97 2.6.2 Release into the Environment 98 2.6.2.1 Dispersion 98 2.6.2.2 Dissolution 99 2.6.2.3 Emulsification 99 2.6.2.4 Evaporation 99 2.6.2.5 Leaching 100 2.6.2.6 Sedimentation or Adsorption 100 2.6.2.7 Spreading 100 2.6.2.8 Wind 100 References 100 3. Test Methods for Crude Oil and Crude Oil Products 102 3.1 The Need for Test Methods 104 3.2 Chemical and Physical Properties of Crude Oil and Crude Oil Products 107 3.2.1 Adhesion 108 3.2.2 Biological Oxygen Demand 109 3.2.3 Boiling Point Distribution 109 Contents vii 3.2.4 Chemical Dispersability 110 3.2.5 Density, Specific Gravity, and API Gravity 111 3.2.6 Emulsion Formation 112 3.2.7 Evaporation 113 3.2.8 Flash Point and Fire Point 114 3.2.9 Fractionation 115 3.2.10 Leachability and Toxicity 116 3.2.11 Metals Content 116 3.2.12 Pour Point and Cloud Point 117 3.2.13 Solubility in Aqueous Media 117 3.2.14 Sulfur Content 117 3.2.15 Surface Tension and Interfacial Tension 118 3.2.16 Total Petroleum Hydrocarbons 118 3.2.17 Viscosity 119 3.2.18 Volatility 120 3.2.19 Water Content 120 3.2.20 Weathering Processes 121 3.3 Petroleum Group Analysis 122 3.3.1 Thin Layer Chromatography 123 3.3.2 Immunoassay 124 3.3.3 Gas Chromatography 124 3.3.4 High Performance Liquid Chromatography 127 3.3.5 Gas Chromatography-Mass Spectrometry 128 3.4 Other Analytical Methods 129 3.4.1 Infrared Spectroscopy 129 3.4.2 Gravimetry 130 3.5 Properties and Analysis of Crude Oil Products 131 3.5.1 Gaseous Products 131 3.5.2 Liquid Products 133 3.5.3 Solid Products 133 References 137 4. The Nature of Oil Spills 141 4.1 Environmental Effects of Crude Oil Refining 141 4.1.1 Gases 142 4.1.2 Liquids 145 4.1.3 Solids 148 4.2 Understanding Spills of Crude Oil and Crude Oil Products 150 4.2.1 Types of Spills 154 4.2.2 Composition of a Spill 154 4.2.3 Dangers of a Spill in the Workplace 155 4.2.4 Causes of Crude Oil Spills 156 4.2.4.1 Transportation 156 4.2.4.2 Errors by Personnel 156 4.2.4.3 Equipment Breakdown 157 4.2.4.4 Natural Disasters 157 4.2.4.5 Acts of Terrorism, War, Vandalism, or Illegal Dumping 157 4.3 Entry into the Environment and Toxicity 158 4.3.1 Entry into the Environment 160 4.3.1.1 Dispersion 160 4.3.1.2 Dissolution 160 viii Petroleum Biodegradation and Oil Spill Bioremediation 4.3.1.3 Emulsification 161 4.3.1.4 Evaporation 161 4.3.1.5 Leaching 161 4.3.1.6 Sedimentation or Adsorption 161 4.3.1.7 Spreading 162 4.3.1.8 Wind 162 4.3.2 Toxicity 162 4.3.2.1 Lower Boiling Constituents 163 4.3.2.2 Higher Boiling Constituents 165 4.3.2.3 Wastewater 166 4.4 General Methods for Soil and Groundwater Remediation 167 4.4.1 Bioremediation 168 4.4.2 Containment 170 4.4.3 Dredging or Excavation 170 4.4.4 In situ Oxidation 171 4.4.5 Metals Removal 172 4.4.6 Nanoremediation 173 4.4.7 Pump and Treat 174 4.4.8 Soil Vapor Extraction 174 4.4.9 Solidification and Stabilization 175 4.4.10 Surfactant Enhanced Aquifer Remediation 176 4.4.11 Thermal Desorption 176 4.5 Remediation Management 178 References 179 5. Overview of Oil Spill Clean Up Methods 181 5.1 Types of Effluents 184 5.1.1 Gaseous Effluents 185 5.1.1.1 Liquefied Petroleum Gas 187 5.1.1.2 Natural Gas 188 5.1.1.3 Refinery Gas 189 5.1.1.4 Sulfur Oxides, Nitrogen Oxides, Hydrogen Sulfide, Carbon Dioxide 191 5.2 Environmental Effects 191 5.2.1 Gaseous Effluents 191 5.2.2 Liquid Effluents 192 5.2.2.1 Naphtha 193 5.2.2.2 Wastewater 201 5.2.3 Solid Effluents 202 5.2.3.1 Residua and Asphalt 204 5.2.3.2 Coke 207 5.2.3.3 Particulate Matter 209 5.3 Oil Spill Cleanup at Sea 209 5.3.1 Oil Booms 209 5.3.2 Skimmers 210 5.3.3 Sorbents 211 5.3.4 Burning In situ 212 5.3.5 Dispersants 214 5.3.6 Hot Water and High-Pressure Washing 214 5.3.7 Chemical Stabilization 215 Contents ix 5.4 Methods for Oil Spill Cleanup on Land 215 5.4.1 Physical Methods 216 5.4.2 Chemical Methods 216 5.5 Bioremediation 217 5.5.1 Importance of Bioremediation 218 5.6 Issues Related to Use of Bioremediation Technologies 219 5.6.1 Environmental 219 5.6.2 Health 220 5.6.3 Process Evaluation 220 5.6.3.1 Feasibility Assessment 221 5.6.3.2 Bioremediation Services 222 5.6.3.3 Barriers to Commercialization 224 5.6.3.4 Supporting Research and Development 224 5.6.3.5 Technical Regulations 225 5.6.3.6 Economic Assessment 225 5.6.3.7 Potential for Future Implementation 226 References 227 PART II: Bioremediation, Biodegradation, and Site Cleanup 6. Bioremediation and Biodegradation 231 6.1 The Origin of Bioremediation 238 6.2 The Mechanism of Bioremediation 240 6.3 Types of Bioremediation 248 6.3.1 Natural Bioremediation 248 6.3.2 Traditional Bioremediation 249 6.3.3 Enhanced Bioremediation 250 6.3.4 Monitored Natural Attenuation 251 6.4 Factors that Affect Bioremediation 252 6.4.1 Chemistry 253 6.4.2 Types of Microbes 254 6.4.3 Types of Contaminants 256 6.4.3.1 Physical Properties 257 6.4.3.2 Chemical Properties 258 6.4.3.3 Site Specific Issues 259 6.4.3.3.1 Geology of the Site 260 6.4.3.3.2 Chemistry of the Site 260 6.5 Site Remediation 261 6.5.1 Method Parameters 261 6.5.2 In situ and ex situ Bioremediation 261 6.5.3 Biostimulation and Bioaugmentation 264 6.5.4 Miscellaneous Processes 265 6.5.4.1 Bioslurping 265 6.5.4.2 Biosparging 265 6.5.4.3 Biosurfactant Treatment 266 6.5.4.4 Bioventing 266 6.5.4.5 Rhizosphere Bioremediation 266 6.6 Bioremediation of Land Ecosystems 267 6.7 Bioremediation of Water Ecosystems 273 References 276