Oil Spill Environmental Forensics

Fingerprinting and Source Identification

By: Scott Stout, Zhendi Wang

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Hardcover | 14 December 2006

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620 Pages

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Oil Spill Environmental Forensics provides a complete view of the various forensic techniques used to identify the source of an oil spill into the environment. The forensic procedures described within represent various methods from scientists throughout the world. The authors explore which analytical and interpretative techniques are best suited for a particular oil spill project.

This handy reference also explores the use of these techniques in actual environmental oil spills. Famous incidents discussed include the Exxon Valdez incident in 1989 and the Guanabara Bay, Brazil 2000. The authors chronicle both the successes and failures of the techniques used for each of these events.

Dr. Zhendi Wang is a senior research scientist and Head of Oil Spill Research of Environment Canada, working in the oil and toxic chemical spill research field. He has authored over 270 academic publications and won a number of national and international scientific honors and awards. Dr. Wang is a member of American Chemical Society (ACS), the Canadian Society for Chemistry (CSC), and the International Society of Environmental Forensics (ISEF).

International experts show readers the forensic techniques used in oil spill investigations
Provides the theoretical basis and practical applications for investigative techniques
Contains numerous case studies demonstrating proven technique

Industry Reviews

Explored are the analytical and interpretative techniques best suited for a particular oil spill project. The book also examines the use of these techniques in actual environmental oil spills and chronicles the successes and failures of the techniques used for each of these events.-Petroleum Review, February 2007

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Non-Fiction Engineering & Technology Environmental Science Social Services & Welfare Crime & Criminology Criminal Investigation & Detection Forensic Science

Preface	p. xlvii
Contributors	p. xlix
Chemical Fingerprinting of Spilled or Discharged Petroleum - Methods and Factors Affecting Petroleum Fingerprints in the Environment	p. 1
Introduction	p. 1
Methods for Chemical Fingerprinting Petroleum	p. 3
Historical Perspective	p. 3
Tier 1 - Chemical Fingerprinting via GC/FID	p. 6
Tier 2 - Chemical Fingerprinting via GC/MS	p. 7
Polycyclic Aromatic Hydrocarbons	p. 8
Petroleum Biomarkers	p. 9
Quality Assurance and Quality Control	p. 10
Quality Control	p. 10
Quality Assurance	p. 10
Factors Controlling the Chemical Fingerprints of Spilled or Discharged Petroleum	p. 11
Primary Control - Crude Oil Genesis	p. 13
Secondary Controls - Petroleum Refining	p. 18
Gasoline	p. 21
Distillate Fuels	p. 22
Residual Fuels	p. 27
Lubricating Oils	p. 28
Oily Waste/Bilge Water Discharges	p. 28
Tertiary Controls - Weathering	p. 29
Evaporation	p. 30
Dissolution	p. 32
Biodegradation	p. 32
Photooxidation	p. 34
Mousse Formation	p. 34
De-Waxing and Wax Enrichment	p. 34
Tertiary Controls-Mixing with "Background"	p. 36
What Is "Background"?	p. 36
Recognizing and Establishing Background	p. 37
Naturally Occurring Background Hydrocarbons	p. 37
Vascular Plant and Algal Debris	p. 38
Particulate Coal and Wood Charcoal	p. 39
Natural Oil Seeps	p. 41
Anthropogenic Background Hydrocarbons	p. 41
Urban and River Runoff	p. 42
Summary	p. 43
References	p. 45
Spill Site Investigation in Environmental Forensic Investigation	p. 55
Introduction	p. 55
Environmental Site Characterization and Reconnaissance Survey	p. 55
Site Entry and Safety Issues during the Emergency Response Phase	p. 57
Management of Safety	p. 57
Risk Assessment and Characterization	p. 58
Chemical Toxicity of the Spilled Oil	p. 59
Working Environment Safety	p. 60
Personal Protective Equipment (PPE)	p. 60
Determination of Geographic Boundary and Definition of Different Zones within the Affected Area: 1. Terrestrial Oil Spills	p. 61
Determination of Geographic Boundary and Definition of Different Zones within the Affected Area: 2. Marine/Coastal Waterborne Oil Spills	p. 62
Collection of Physical, Ecological, and Environmental Data	p. 63
Sampling Plan and Design: 1. Spills with Known Source	p. 64
Water Column Sampling	p. 64
Oil Source Sampling	p. 65
Sampling on Land	p. 65
Sampling Plan Design	p. 65
Sampling Plan and Design: 2. "Mystery" Spills	p. 66
Data Management	p. 67
Conclusions	p. 71
References	p. 71
Petroleum Biomarker Fingerprinting for Oil Spill Characterization and Source Identification	p. 73
Introduction	p. 73
Analytical Methodologies for Petroleum Biomarker Fingerprinting	p. 74
Petroleum Biomarker Families	p. 74
Acyclic Terpenoids or Isoprenoids	p. 75
Cyclic Terpenoids	p. 75
Labeling and Nomenclature of Biomarkers	p. 77
Stereoisomers	p. 79
Asymmetric (or Chiral) Carbons and [Alpha] and [Beta] Stereoisomers	p. 80
R and S Stereoisomers of Cyclic Biomarkers	p. 81
Analysis Methods for Biomarker Fingerprinting	p. 81
Capillary Gas Chromatography - Mass Spectrometry (GC-MS)	p. 83
Benchtop Quadrupole GC-MS	p. 84
Scan Mode	p. 84
Selected Ion Monitoring (SIM) Mode	p. 84
Example Benchtop GC-MS Conditions (EC Oil Spill Research Laboratory)	p. 85
Example Benchtop GC-MS Conditions (Petrobras Geochemistry Laboratory)	p. 85
Triple Quadrupole GC-MS-MS	p. 85
Mass Spectra and Identification of Biomarkers	p. 86
Fingerprinting Petroleum Biomarkers	p. 90
Biomarkers in Crude Oils	p. 90
Biomarkers in Petroleum Products	p. 99
Biomarkers in Lubricating Oils	p. 101
Biomarkers in Oil Fractions with Different Carbon Number Range	p. 104
Aromatic Steranes in Oils and Petroleum Products	p. 104
Sesquiterpanes in Oils and Petroleum Products	p. 109
Diamondoid Compounds in Oils and Lighter Petroleum Products	p. 114
Application of Biomarker Fingerprintings to Oil Spill Studies	p. 117
Source-Specific Biomarkers	p. 121
	p. 125
Diagnostic Ratios of Biomarkers	p. 126
Cross-Plots of Biomarkers	p. 128
Effects of Weathering on Biomarker Fingerprinting	p. 130
Processes Affecting the Fate and Behavior of Spilled Oil	p. 130
Weathering Effects on Biomarkers Fingerprinting	p. 132
Biodegradation of Biomarkers in Spilled Oil	p. 133
Determination of Weathered Percentages Using Biomarkers	p. 134
Case Study: Source Identification of a Harbor Spill by Forensic Fingerprinting of Biomarkers	p. 134
Product Type-Screening	p. 134
Characterization of Bicyclic Sesquiterpanes	p. 135
Confirmation of Source Identification by Quantitative Evaluation of Alkylated PAHs and Pentacyclic Terpanes and Steranes	p. 135
Conclusions	p. 138
References	p. 140
Characterization of Polycyclic Aromatic Sulfur Heterocycles for Source Identification	p. 147
Introduction	p. 147
Sulfur Compounds in Crude Oil and Petroleum Products	p. 148
Influence of Refinery Processes on PASH Patterns	p. 150
Stability of Polycyclic Aromatic Sulfur Heterocycles in the Environment	p. 152
Petroleum PASH Analysis Techniques	p. 155
Selective Detection in Gas Chromatography	p. 156
Flame Photometric Detection (FPD)	p. 156
Atomic Emission Detection (AED)	p. 157
Sulfur Chemiluminescence Detection (SCD)	p. 157
Mass-Selective Detection (MSD)	p. 157
Class Separation of PAH and PASH	p. 157
Comprehensive Two-Dimensional Gas Chromatography	p. 158
Quantification of PASH	p. 158
Petroleum PASH Markers in Environmental Forensic Investigations	p. 159
PASHs as Source Markers	p. 160
PASHs as Weathering Markers	p. 162
Conclusions	p. 164
References	p. 164
Oil Spill Identification by Comprehensive Two-Dimensional Gas Chromatography (GC x GC)	p. 169
Introduction	p. 169
The Need for High-Resolution Separations	p. 169
Multidimensional Methods	p. 170
Comprehensive Two-Dimensional Gas Chromatography (GC x GC)	p. 171
Modulation Techniques	p. 172
Detectors	p. 172
Data Processing	p. 173
GC x GC Chromatogram	p. 174
Peak Identity and Chromatogram Structure	p. 175
GC x GC Petroleum Applications	p. 180
Applications of GC x GC to Fingerprint Oil Spills	p. 181
Mobile Bay Marine Diesel Fuel Spill	p. 181
West Falmouth No. 2 Fuel Oil Spill	p. 184
Winsor Cove No. 2 Fuel Oil Spill	p. 187
Buzzards Bay No. 6 (Bunker C) Spill	p. 191
Oil Seeps, Santa Barbara, CA, USA	p. 196
Conclusion	p. 201
Acknowledgments	p. 202
References	p. 202
Application of Stable Isotope Ratios in Spilled Oil Identification	p. 207
Introduction	p. 207
Isotope Ratios and Their Measurement	p. 207
Bulk Isotope Ratios	p. 210
Compound-Specific Isotope Analysis (CSIA)	p. 214
Experimental Considerations	p. 220
Weathering	p. 220
Other Isotopes	p. 224
Conclusions	p. 224
References	p. 225
Emerging CEN Methodology for Oil Spill Identification	p. 229
Introduction	p. 230
Scope of the CEN Methodology	p. 231
Strategy for Identifying Oil Spills	p. 231
Tiered Levels of Analysis and Data Treatment	p. 233
Decision Chart for Identifying Oil Spills	p. 233
Visual Characterization and Preparation/Cleanup of Oil Samples	p. 233
Level 1 - GC/FID Screening	p. 235
Evaluation of Weathering	p. 236
Level 2 - GC/MS Fingerprinting	p. 237
Diagnostic Ratios from GC/MS Fingerprinting	p. 237
Diagnostic Ratios Derived from Alkylated Polycyclic Aromatic Compounds	p. 238
Diagnostic Ratios Derived from Petroleum Biomarkers	p. 239
Optional Diagnostic Ratios Derived from Sesquiterpanes	p. 240
Level 3 - Treatment of Results	p. 245
Comparison of Oil Samples Using Diagnostic Ratios	p. 245
Criteria for Selecting, Eliminating, and Evaluating Diagnostic Ratios	p. 245
Repeatability Limit and Critical Difference	p. 246
Elimination of Diagnostic Ratios Using Signal-to-Noise (S/N) Test	p. 246
Elimination of Diagnostic Ratios Using Duplicate Analyses	p. 248
Optional Comparison of Diagnostic Ratios Using Multivariate Statistics	p. 249
Final Evaluation and Conclusions	p. 250
The CEN Methodology in Practice: A Case Study	p. 251
The Spill Case	p. 251
GC/FID Screening	p. 251
GC/MS Fingerprinting	p. 251
Evaluation and Comparison of Diagnostic Ratios	p. 251
Summary	p. 254
Acknowledgment	p. 255
References	p. 255
Advantages of Quantitative Chemical Fingerprinting in Oil Spill Source Identification	p. 257
Introduction	p. 257
Qualitative Fingerprinting Methods	p. 258
Shortcomings of Qualitative Fingerprinting	p. 260
Weathered Oils	p. 260
Genetically Similar Oils	p. 260
Qualitatively Similar Oils	p. 261
Mixing	p. 261
Quantitative Fingerprinting Methods	p. 263
Semiquantitative versus Fully Quantitative Methods	p. 263
Data Generation for Fully Quantitative Fingerprinting	p. 265
Sample Collection	p. 265
Sample Preparation	p. 266
GC/FID Analysis	p. 266
GC/MS Analysis	p. 268
Data Quality	p. 269
Selection of Diagnostic Indices	p. 269
Source Identification Protocols for Quantitative Fingerprinting Data	p. 272
Unraveling Mixed Source Oils Using Quantitative Fingerprinting Data	p. 276
Two-Component Mixing Models	p. 276
Case Study 1	p. 277
Case Study 2	p. 279
Mixing Model Case Study 2	p. 284
Summary	p. 289
References	p. 290
A Multivariate Approach to Oil Hydrocarbon Fingerprinting and Spill Source Identification	p. 293
Introduction	p. 293
Multivariate Methods and Oil Fingerprinting	p. 294
Integrated Multivariate Oil Fingerprinting (IMOF)	p. 296
Sample Preparation and Chemical Analysis	p. 297
Sample Preparation	p. 297
Analytical Methods	p. 298
Fluorescence Spectroscopy	p. 298
GC-MS	p. 299
Quality Assurance and Quality Control (QA/QC)	p. 301
Data Preprocessing	p. 302
Partial GC-MS/SIM Chromatograms	p. 303
Baseline Removal	p. 303
Retention Time Alignment	p. 304
Normalization	p. 306
Diagnostic Ratios	p. 306
Preprocessing of Fluorescence Spectra	p. 307
Multivariate Statistical Data Analysis	p. 308
Multilinear Models	p. 310
Two-Way Case	p. 310
Higher-Order Arrays	p. 311
Variable Selection and Scaling	p. 312
Data Evaluation	p. 314
Visual Inspection of Score and Loading Plots	p. 315
Numerical Comparisons and Statistical Tests	p. 317
Conclusions and Perspectives	p. 319
Acknowledgments	p. 321
References	p. 322
Chemical Heterogeneity of Modern Marine Residual Fuel Oils	p. 327
Introduction	p. 327
Historical Perspective	p. 328
Production of Heavy Fuel Oils	p. 328
Marine Fuel Nomenclature and Classification	p. 329
Forensic Chemistry Considerations	p. 330
General Chemical Fingerprinting	p. 330
Samples and Analytical Methods	p. 332
General Features of Modern Residual Marine Fuel Oils	p. 332
Molecular Variability among Modern Residual Fuel Oils	p. 336
Petroleum Biomarkers	p. 336
Polycyclic Aromatic Hydrocarbons	p. 338
Distinguishing Heavy Fuel Oils from Crude Oil	p. 343
Conclusion	p. 346
References	p. 346
Biodegradation of Oil Hydrocarbons and Its Implications for Source Identification	p. 349
Introduction	p. 349
Biochemistry of Petroleum Biodegradation	p. 349
Aerobic Biodegradation of Hydrocarbons	p. 351
Anaerobic Biodegradation of Hydrocarbons	p. 355
Subsurface Biodegradation of Petroleum	p. 357
The Biodegradation of Hopanes and the Formation of 25-Norhopanes	p. 360
Factors Limiting Biodegradation	p. 362
Microbial Ecology of Petroleum Biodegradation	p. 365
The Succession of Microbial Communities	p. 365
Deep Subsurface Ecology	p. 367
Aerobic Respiration	p. 367
Anaerobic Respiration	p. 368
Conclusions; Implications of Biodegradation on Identification	p. 369
References	p. 370
Identification of Hydrocarbons in Biological Samples for Source Determination	p. 381
Introduction	p. 381
Determination of the Primary Route of Hydrocarbon Accumulation by Biota	p. 382
Catabolic Degradation of Hydrocarbons Accumulated by Biota	p. 387
Catabolic Degradation of PAH	p. 387
Effects of Catabolism on PAH Accumulation, Persistence, and Depuration	p. 390
Modes of Toxic Action of Accumulated Hydrocarbons	p. 393
Case Study: The Exxon Valdez Oil Spill	p. 396
Summary	p. 398
References	p. 398
Trajectory Modeling of Marine Oil Spills	p. 405
Introduction	p. 405
Forecasting and Hindcasting Oil Spill Movement	p. 406
Oil Spill Transport	p. 407
Wind	p. 409
Currents	p. 411
Turbulent Diffusion	p. 413
Evolution of an Oil Spill	p. 413
Spreading	p. 413
Oil Weathering	p. 414
Conclusions and Challenges	p. 416
Acknowledgments	p. 416
References	p. 416
Oil Spill Remote Sensing: A Forensic Approach	p. 419
Introduction	p. 419
Visible Indications of Oil	p. 420
Optical Sensors	p. 420
Visible	p. 420
Infrared	p. 422
Ultraviolet	p. 423
Night Vision Cameras	p. 423
Laser Fluorosensors	p. 423
Microwave Sensors	p. 426
Radiometers	p. 426
Radar	p. 426
Microwave Scatterometers	p. 428
Determination of Slick Thickness	p. 428
Visual Thickness Indications	p. 428
Theoretical Approaches	p. 429
Literature Review of Visual Indications of Oil Slick Thickness	p. 429
Oil Slick-Thickness Relationships in Remote Sensors	p. 431
Specific Oil-Thickness Sensors	p. 432
Acoustic Systems	p. 435
Satellite Remote Sensing	p. 435
Detection of Oil under Ice	p. 436
Real-Time Displays and Printers	p. 438
Future Trends	p. 438
References	p. 439
Advances in Forensic Techniques for Petroleum Hydrocarbons: The Exxon Valdez Experience	p. 449
Introduction	p. 449
Identification of Hydrocarbon Sources in PWS	p. 450
Multiple Sources of Hydrocarbons	p. 450
Petrogenic Hydrocarbons	p. 451
Biogenic Hydrocarbons	p. 453
Pyrogenic Hydrocarbons	p. 453
Composition of Exxon Valdez Crude and Its Weathering Products	p. 453
Bulk Composition and Trace Chemistry	p. 453
Weathering Trends	p. 457
Data Sources	p. 457
Major Fraction Trends	p. 457
PAH Trends	p. 457
Mass Loss during Weathering	p. 458
Resolution of Inputs to the Natural Background	p. 458
Hydrocarbon Source Allocations	p. 462
Source Allocation Models	p. 462
Qualitative Allocation Models	p. 464
Quantitative Models	p. 464
PAH Ratios	p. 464
Statistical Models	p. 465
Statistical Models	p. 466
Multivariate Methods - Constrained Least Squares	p. 466
Multivariate Analysis - Partial Least Squares	p. 468
Total Organic Carbon (TOC) Constraints on Source Allocations	p. 468
Allocation of Anthropogenic Sources of PAH	p. 469
Identification of Hydrocarbons in Biological Samples	p. 470
Applications of Forensic Methods to Assessments of Oil Bioavailability	p. 477
PAH Uptake in Biota	p. 477
Passive Sampling of PAH in Water	p. 481
Biological Markers	p. 481
Summary	p. 482
Acknowledgments	p. 483
References	p. 483
Case Study: Oil Spills in the Strait of Malacca, Malaysia	p. 489
Strait of Malacca, Malaysia: Introduction	p. 489
Hydro-Oceanographic Condition of the Strait	p. 489
Ship Traffic in the Strait of Malacca: Historical and Present	p. 491
Chronic and Acute Oil Spill Events in the Strait	p. 491
Contribution of Oil Pollution Sources in Malaysia	p. 491
Methodology	p. 492
Sample Collection	p. 492
Source Petroleum	p. 492
Tar-Ball Samples	p. 492
Sediment Samples	p. 492
Street Dust Samples	p. 493
Asphalt Samples	p. 494
Fresh Crankcase Oil	p. 494
Used Crankcase Oil	p. 495
Automobile Tire Rubber	p. 495
Aerosol Samples	p. 495
Analytical Procedure	p. 495
Chemicals	p. 495
Extraction and Fractionation	p. 496
Instrumental Analysis	p. 496
Analysis of Alkanes and Hopanes	p. 496
N-Cyclohexyl-2-Benzothiozolamine (NCBA)	p. 497
Analysis of PAHs	p. 497
Establishment and Application of Biomarker Analysis for Source Identification of Oil Pollution Sources in the Strait of Malacca	p. 498
Case Study 1: Development of the Analytical Method for Oil Pollution Source Identification Using Biomarkers in the Strait of Malacca	p. 498
Weathering of Tar Balls	p. 499
The Application of Molecular Markers for Source Identification of Tar-Ball Pollution in Malaysia	p. 501
Case Study 2: Distribution and Sources of Polycyclic Aromatic Hydrocarbons (PAHs) in Rivers and Estuaries in Malaysia	p. 502
Conclusions and Future Scenario	p. 502
References	p. 503
Evaluation of Hydrocarbon Sources in Guanabara Bay, Brazil	p. 505
Guanabara Bay and Hydrocarbon Apportioning	p. 505
Regional Setting	p. 506
January 2000 Heavy Fuel Oil Spill	p. 506
Methodology for Hydrocarbon Determination and Source Evaluation	p. 507
Sampling Design	p. 507
Chemical Analysis	p. 508
Sediment Sample Extraction	p. 508
Extract Cleanup	p. 509
PAH Analysis of Sediment Samples	p. 509
Biomarkers	p. 510
Source Identification Techniques	p. 510
PAH Diagnostic Ratios	p. 510
PAH Multivariate Statistical Analysis	p. 511
Biomarker Diagnostic Ratios	p. 511
Hydrocarbon Results for Guanabara Bay Sediments	p. 511
PAH Quantification and Distribution	p. 511
Hydrocarbon Source Identification	p. 514
PAH Diagnostic Ratios	p. 514
PAH Principal Component Analysis	p. 525
Biomarker Diagnostic Ratios	p. 527
Conclusions	p. 531
Acknowledgments	p. 533
References	p. 534
Index	p. 537
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Oil Spill Environmental Forensics

Fingerprinting and Source Identification

At a Glance

New Edition

Hardcover

Industry Reviews

Shipping

How to return your order

Defective items

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