With petroleum-related spills, explosions, and health issues in the headlines almost every day, the issue of remediation of petroleum and petroleum products is taking on increasing importance, for the survival of our environment, our planet, and our future.
Karuna Arjoon graduated in 2009 from the University of Trinidad and Tobago with a Master of Philosophy and a Bachelor of Science from the University of the West Indies in 2004. She has been at the University of Trinidad and Tobago for the past four years at various academic positions. Karuna has provided consultant services for various international companies and has affiliations with The National Association of Corrosion Engineers.
Table of ContentsPreface 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
2 Petroleum Composition and Properties 39
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 Specifi c Gravity 63
3.2 Elemental (Ultimate) Analysis 64
3.3 Chromatographic Fractionation 65
3.4 Liquefaction and Solidifi cation 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 Refi nery Products and By-Products 79
1 Introduction 79
2 Refi nery Products 81
2.1 Liquefi ed 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 Refi nery 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 Liquefi ed Petroleum Gas 118
2.2 Natural Gas 121
2.3 Refi nery Gas 125
3 Environmental Effects 129
4 Analysis 134
4.1 Calorifi c 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 (Specifi c 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 (Specifi c 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
6 Composition and Properties of Solid Products 183
1 Introduction 183
2 Residua and Asphalt 184
2.1 Acid Number 187
2.2 Asphaltene Content 188
3.3 Carbon Disulfi de Insoluble Constituents 189
2.4 Composition 190
2.5 Density (Specifi c 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 Coke 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, Specifi c 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 Specifi c 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
Contents xi
10 Biodegradation of Naphtha and Gasoline 361
1 Introduction 361
2 Identity and Origin 361
3 Remediation 363
3.1 Site Remediation 364
3.2 In-Situ Air Stripping 369
3.3 Pump-and-Treat Systems 370
3.4 Vacuum Enhanced Recovery 370
3.5 Single-Phase Vacuum Extraction 371
3.6 Dual-Phase Vacuum Extraction 371
3.7 Surfactant Enhanced Aquifer Redemption 371
3.8 In Situ Chemical Oxidation 371
3.8.1 Hydrogen Peroxide/Fenton--
Reagent 371
3.8.2 Permanganates 372
3.9 In Situ-Enhanced Bioremediation 372
3.10 Monitored Natural Attenuation 376
4 BTEX and MTBE 377
4.1 BTEX 377
4.2 Methyl Tert-Butyl Ether 380
5 References 382
11 Biodegradation of Kerosene and Diesel 385
1 Introduction 385
2 Identity and Origin of Kerosene and Diesel 387
3 Bioremediation 389
3.1 Kerosene 389
3.2 Diesel Fuel 391
3.3 Diesel Fuel Additives 401
4 Jet Fuel 402
5 References 404
12 Biodegradation of Fuel Oil 413
1 Introduction 413
2 Identity and Origin of Fuel Oil 416
2.1 Production 417
2.2 Properties 419
3 Biodegradation 421
4 References 427
xii Contents
13 Biodegradation of Lubricating Oil 431
1 Introduction 431
2 Identity and Origin of Lubricating Oil 434
3 Composition and Properties of Lubricating Oil 436
3.1 Thermal Stability of Lubricating Oils 437
3.2 Environmental Aspects of Lubricating Oil Use 438
4 Biodegradation of Lubricating Oils 438
4.1 Petroleum-Based Oils 440
4.2 Synthetic Lubricating Oil 442
4.3 Used Lubricating Oil 443
4.4 Vegetable Oils 448
5 Bioremediation --The Challenge 452
6 Conclusion 453
7 References 453
14 Biodegradation of Residua and Asphalt 463
1 Introduction 463
2 Identity and Origin of Residua and Asphalt 467
2.1 Residua 467
2.2 Asphalt 467
3 Biodegradation of Residua and Asphalt 469
3.1 Residua 470
3.2 Asphalt 471
3.3 Asphaltene Constituents 473
4 References 477
15 Bioremediation Methods 483
1 Land Ecosystems 483
1.1 Site Evaluation 486
1.2 Soil Evaluation 489
1.2.1 Physical Properties 489
1.2.2 Chemical Properties 492
1.2.3 Biological Properties 493
1.3 Effect of Temperature 496
1.4 Effect of pH 497
1.5 Effect of Salinity 498
Contents xiii
2 Water Ecosystems 498
2.1 Biodegradation 501
2.2 Bioremediation 502
2.2.1 Effect of Temperature 503
2.2.2 Effect of Oxygen 505
2.2.3 Nutrients 505
2.2.4 Effect of Petroleum Characteristics 506
2.2.5 Effect of Prior Exposure 506
2.2.6 Effect of Dispersants 506
2.2.7 Effect of Flowing Water 506
2.2.8 Effect of Deep-Sea Environments 507
3 References 507
16 The Future of Bioremediation 515
1 Introduction 515
2 Status 517
2.1 Conventional Bioremediation 517
2.2 Enhanced Bioremediation 519
2.3 Bioremediation in Extreme Environments 522
3 Advantages and Disadvantages 524
4 Conclusion 526
5 References 528
Glossary 535
Conversion Factors 555
Index 559
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