Bioremediation of Petroleum and Petroleum Products Scrivener Publishing 100 Cummings Center, Suite 541J Beverly, MA 01915-6106 Publishers at Scrivener Martin Scrivener ([email protected]) Phillip Carmical ([email protected]) Bioremediation of Petroleum and Petroleum Products James G. Speight CD&W Inc., Laramie, Wyoming, USA Karuna K. Arjoon KKA Associates, California, Trinidad and Tobago Scrivener WILEY Copyright © 2012 by Scrivener Publishing LLC. All rights reserved. Co-published by John Wiley & Sons, Inc. Hoboken, New Jersey, and Scrivener Publishing LLC, Salem, Massachusetts. Published simultaneously in Canada. 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Cover design by Kris Hackerott Library of Congress Cataloging-in-Publication Data: ISBN 978-0-470-93849-2 Printed in the United States of America 10 9 8 7 6 5 4 3 21 Contents Preface xv 1 Introduction to Bioremediation 1 1 Introduction 1 2 Principles of Bioremediation 7 3 Bioremediation and Biodegradation 10 3.1 Natural Bioremediation 10 3.2 Traditional Bioremediation Methods 11 3.3 Enhanced Bioremediation Treatment 12 3.4 Biostimulation and Bioaugmentation 12 3.5 In Situ and Ex Situ Bioremediation Techniques 13 4 Mechanism of Biodegradation 15 4.1 Chemical Reactions 15 4.2 Kinetic Aspects 19 4.3 Effect of Salt 20 5 Bioremediation Methods 22 5.1 Method Parameters 23 5.2 In Situ and Ex Situ Bioremediation 24 5.3 Biostimulation and Bioaugmentation of Contaminated Sites 25 5.4 Monitored Natural Attenuation 25 5.5 Soil Vapor Extraction, Air Sparging, and Bioventing 26 5.6 Use of Biosurfactants 28 5.7 Rhizosphere Bioremediation 28 5.8 Bioengineering in Bioremediation 29 6 Test Methods for Biodegradation 30 7 References 31 v vi CONTENTS Pe: troleui m Composition and Properties 39 2 1 Introduction 39 2 Composition 46 2.1 Elemental Composition 47 2.2 Chemical Composition 50 2.3 Composition by Volatility 52 2.4 Composition by Fractionation 55 2.5 Composition by Spectroscopy 57 2.5.1 Infrared Spectroscopy 58 2.5.2 Nuclear Magnetic Resonance 58 2.5.3 Mass Spectrometry 59 2.5.4 Other Techniques 61 3 Properties 62 3.1 Density and Specific Gravity 63 3.2 Elemental (Ultimate) Analysis 64 3.3 Chromatographie Fractionation 65 3.4 Liquefaction and Solidification 67 3.5 Metals Content 68 3.6 Surface and Interfacial Tension 69 3.7 Viscosity 71 3.8 Volatility 74 4 References 76 3 Refinery Products and By-Products 79 1 Introduction 79 2 Refinery Products 81 2.1 Liquefied Petroleum Gas 90 2.2 Naphtha, Gasoline, and Solvents 92 2.3 Kerosene and Diesel Fuel 94 2.4 Fuel Oil 95 2.5 Lubricating Oil 98 2.6 White Oil, Insulating Oil, Insecticides 100 2.7 Grease 101 2.8 Wax 102 2.9 Asphalt 104 2.10 Coke 105 3 Refinery Chemicals 106 3.1 Spent Caustic 106 CONTENTS vii 3.2 Spent Acids 107 3.3 Spent Catalysts 109 3.3.1 Demet 113 3.3.2 Met-X 113 4 References 113 4 Composition and Properties of Gaseous Products 115 1 Introduction 115 2 Gaseous Products 118 2.1 Liquefied Petroleum Gas 118 2.2 Natural Gas 121 2.3 Refinery Gas 125 3 Environmental Effects 129 4 Analysis 134 4.1 Calorific Value (Heat of Combustion) 136 4.2 Composition 136 4.3 Density 141 4.4 Relative density 141 4.5 Sulfur 142 4.6 Volatility and Vapor Pressure 143 5 References 143 5 Composition and Properties of Liquid Products 147 1 Introduction 147 2 Naphtha 148 2.1 Composition 153 2.2 Density (Specific Gravity) 158 2.3 Evaporation Rate 158 2.4 Flash Point 159 2.5 Odor and Color 159 2.6 Volatility 160 2.7 Environmental Impact 161 3 Fuel Oil 162 3.1 Asphaltene Content 164 3.2 Composition 165 3.3 Density (Specific Gravity) 167 3.4 Elemental Analysis 168 3.5 Flash Point 172 3.6 Metals Content 172 viii CONTENTS 3.7 Pour Point and Viscosity 173 3.8 Stability 174 3.9 Environmental Impact 175 4 Wastewaters 177 5 References 180 Composition and Properties of Solid Products 183 6 1 Introduction 183 2 Residua and Asphalt 184 2.1 Acid Number 187 2.2 Asphaltene Content 188 3.3 Carbon Disulfide Insoluble Constituents 189 2.4 Composition 190 2.5 Density (Specific Gravity) 192 2.6 Elemental Analysis 195 2.7 Float Test 196 2.8 Softening Point 196 2.9 Viscosity 197 2.10 Weathering 197 2.11 Environmental Impact 197 3 Cokti 199 3.1 Ash 201 3.2 Composition 202 3.3 Density 204 3.4 Dust Control Material 205 3.5 Hardness 205 3.6 Metals 206 3.7 Sulfur 207 3.8 Environmental Impact 207 4 Sludge 208 5 References 210 7 Sample Collection and Preparation 213 1 Introduction 213 2 Petroleum Chemicals 215 3 Sample Collection and Preparation 218 3.1 Soil Sampling 220 3.2 Sampling from an Aqueous Medium 221 CONTENTS ix 3.3 Sample Collection 222 3.3.1 Volatile Compounds 225 3.3.2 Condensate Releases 227 3.3.3 Semi-Volatile and Non-Volatile Compounds 228 3.3.4 Solids 233 3.3.5 Water Samples 236 3.4 Extract Concentration 237 3.5 Sample Cleanup 240 4 Measurement 240 5 Accuracy 242 6 Precision 243 7 Method Validation 245 8 Quality Control and Quality Assurance 252 8.1 Quality Control 253 8.2 Quality Assurance 255 9 Method Detection Limit 256 10 References 256 8 Analytical Methods 259 1 Introduction 259 2 Chemical And Physical Properties 262 2.1 Adhesion 263 2.2 Biological Oxygen Demand 263 2.3 Boiling Point Distribution 264 2.4 Chemical Dispersibility 265 2.5 Density, Specific Gravity, and API Gravity 266 2.6 Emulsion Formation 267 2.7 Evaporation 268 2.8 Fire Point and Flash Point 269 2.9 Fractionation 270 2.10 Leachability and Toxicity 270 2.11 Metals Content 271 2.12 Pour Point 272 2.13 Solubility in Aqueous Media 272 2.14 Sulfur Content 273 2.15 Surface Tension and Interfacial Tension 273 2.16 Total Petroleum Hydrocarbons 274 x CONTENTS 2.17 Viscosity 277 2.18 Volatile Organic Compounds 278 2.19 Water Content 279 3 Petroleum Group Analyses 279 3.1 Thin Layer Chromatography 283 3.2 Immunoassay 284 3.3 Gas Chromatography 285 3.4 High Performance Liquid Chromatography 287 3.5 Gas Chromatography-Mass Spectrometry 288 4 Other Analytical Methods 289 4.1 Total Petroleum Hydrocarbons 289 4.2 Gas Chromatography 290 4.3 Infrared Spectroscopy 294 4.4 Gravimetry 296 4.5 Immunoassay 297 5 References 298 9 Biodegradation of Petroleum 305 1 Introduction 305 2 Biodegradation of Specific Constituents 307 2.1 Alkanes 307 2.2 Aromatic hydrocarbons 309 2.3 Polynuclear Aromatic Hydrocarbons 310 2.4 Phenolic Compounds 316 2.5 Spent Caustic 317 2.6 Wastewater 318 2.7 Chlorinated Compounds 319 3 Petroleum Biodegradation 319 3.1 Effects of Biodegradation 322 3.2 Conditions for Biodegradation 323 3.3 Effect of Nutrients 325 3.4 Effect of Temperature 327 3.5 Effect of Dispersants 329 3.6 Rates of Oil Biodegradation 329 3.7 Effect of Weathering 332 4 Application to Spills 333 4.1 General Application 336 5 References 339