Preface ..................................................... xivii
Contributors ................................................. xlix
1 Chemical Fingerprinting of Spilled or Discharged
Petroleum — Methods and Factors Affecting Petroleum
Fingerprints in the Environment ............................ 1
1.1 Introduction ............................................... 1
1.2 Methods for Chemical Fingerprinting Petroleum .............. 3
1.2.1 Historical Perspective .............................. 3
1.2.2 Tier 1 — Chemical Fingerprinting via GC/FID ......... 6
1.2.3 Tier 2 — Chemical Fingerprinting via GC/MS .......... 7
1.2.3.1 Poly cyclic Aromatic Hydrocarbon ........... 8
1.2.3.2 Petroleum Biomarkers ....................... 9
1.2.4 Quality Assurance and Quality Control .............. 10
1.2.4.1 Quality Control ........................... 10
1.2.4.2 Quality Assurance ......................... 10
1.3 Factors Controlling the Chemical Fingerprints of
Spilled or Discharged Petroleum ........................... 11
1.3.1 Primary Control — Crude Oil Genesis ................ 13
1.3.2 Secondary Controls — Petroleum Refining ............ 18
1.3.2.1 Gasoline .................................. 21
1.3.2.2 Distillate Fuels .......................... 22
1.3.2.3 Residual Fuels ............................ 27
1.3.2.4 Lubricating Oils .......................... 28
1.3.2.5 Oily Waste/Bilge Water Discharges ......... 28
1.3.3 Tertiary Controls — Weathering ..................... 29
1.3.3.1 Evaporation ............................... 30
1.3.3.2 Dissolution ............................... 32
1.3.3.3 Biodegradation ............................ 32
1.3.3.4 Photooxidation ............................ 34
1.3.3.5 Mousse Formation .......................... 34
1.3.3.6 De-Waxing and Wax Enrichment .............. 34
1.3.4 Tertiary Controls—Mixing with "Background" ......... 36
1.3.4.1 What Is "Background"? ..................... 36
1.3.4.2 Recognizing and Establishing Background ... 37
1.3.4.3 Naturally Occurring Background
Hydrocarbons .............................. 37
1.3.4.3.1 Vascular Plant and Algal
Debris ......................... 38
1.3.4.3.2 Particulate Coal and Wood
Charcoal ....................... 39
1.3.4.3.3 Natural Oil Seeps .............. 41
1.3.4.4 Anthropogenic Background Hydrocarbons ..... 41
1.3.4.4.1 Urban and River Runoff ......... 42
1.4 Summary ................................................... 43
References ................................................ 45
2 Spill Site Investigation in Environmental Forensic
Investigation ............................................. 55
2.1 Introduction .............................................. 55
2.2 Environmental Site Characterization and Reconnaissance
Survey .................................................... 55
2.3 Site Entry and Safety Issues during the Emergency
Response Phase ............................................ 57
2.3.1 Management of Safety ............................... 57
2.3.2 Risk Assessment and Characterization ............... 58
2.3.3 Chemical Toxicity of the Spilled Oil ............... 59
2.3.4 Working Environment Safety ......................... 60
2.3.5 Personal Protective Equipment (PPE) ................ 60
2.4 Determination of Geographic Boundary and Definition of
Different Zones within the Affected Area: 1. Terrestrial
Oil Spills ................................................ 61
2.5 Determination of Geographic Boundary and Definition of
Different Zones within the Affected Area: 2. Marine/
Coastal Waterborne Oil Spills ............................. 62
2.6 Collection of Physical, Ecological, and Environmental
Data ...................................................... 63
2.7 Sampling Plan and Design: 1. Spills with Known Source ..... 64
2.7.1 Water Column Sampling .............................. 64
2.7.2 Oil Source Sampling ................................ 65
2.7.3 Sampling on Land ................................... 65
2.7.4 Sampling Plan Design ............................... 65
2.8 Sampling Plan and Design: 2. "Mystery" Spills ............. 66
2.9 Data Management ........................................... 67
2.10 Conclusions ............................................... 71
References ................................................ 71
3 Petroleum Biomarker Fingerprinting for Oil Spill
Characterization and Source Identification ................ 73
3.1 Introduction .............................................. 73
3.2 Analytical Methodologies for Petroleum Biomarker
Fingerprinting ............................................ 74
3.2.1 Petroleum Biomarker Families ....................... 74
3.2.1.1 Acyclic Terpenoids or Isoprenoids ......... 75
3.2.1.2 Cyclic Terpenoids ......................... 75
3.2.2 Labeling and Nomenclature of Biomarkers ............ 77
3.2.2.1 Stereoisomers ............................. 79
3.2.2.2 Asymmetric (or Chiral) Carbons and a and
Я Stereoisomers ........................... 80
3.2.2.3 R and S Stereoisomers of Cyclic
Biomarkers ................................ 81
3.2.3 Analysis Methods for Biomarker Fingerprinting ...... 81
3.2.4 Capillary Gas Chromatography — Mass Spectrometry
(GC-MS) ............................................ 83
3.2.4.1 Benchtop Quadrapole GC-MS ................. 84
3.2.4.1.1 Scan Mode ...................... 84
3.2.4.1.2 Selected Ion Monitoring (SIM)
Mode ........................... 84
3.2.4.1.3 Example Benchtop GC-MS
Conditions (EC Oil Spill
Research Laboratory) ........... 85
3.2.4.1.4 Example Benchtop GC-MS
Conditions (Petrobras
Geochemistry Laboratory) ....... 85
3.2.4.2 Triple Quadrapole GC-MS-MS ................ 85
3.2.5 Mass Spectra and Identification of Biomarkers ...... 86
3.3 Fingerprinting Petroleum Biomarkers ....................... 90
3.3.1 Biomarkers in Crude Oils ........................... 90
3.3.2 Biomarkers in Petroleum Products ................... 99
3.3.3 Biomarkers in Lubricating Oils .................... 101
3.3.4 Biomarkers in Oil Fractions with Different
Carbon Number Range ............................... 104
3.3.5 Aromatic Steranes in Oils and Petroleum Products .. 104
3.3.6 Sesquiterpanes in Oils and Petroleum Products ..... 109
3.3.7 Diamondoid Compounds in Oils and Lighter
Petroleum Products ................................ 114
3.3.8 Application of Biomarker Fingerprintings to Oil
Spill Studies ..................................... 117
3.3.9 Source-Specific Biomarkers ........................ 121
3.3.10 Using Diagnostic Ratios and Cross-Plots of
Biomarkers for Source Identification of Oil
Spills ............................................ 125
3.3.10.1 Diagnostic Ratios of Biomarkers ......... 126
3.3.10.2 Cross-Plots of Biomarkers ............... 128
3.4 Effects of Weathering on Biomarker Р^ефйШ ................ 130
3.4.1 Processes Affecting the Fate and Behavior of
Spilled Oil ....................................... 130
3.4.2 Weathering Effects on Biomarkers Fingerprinting ... 132
3.4.3 Biodegradation of Biomarkers in Spilled Oil ....... 133
3.4.4 Determination of Weathered Percentages Using
Biomarkers ........................................ 134
3.4.5 Case Study: Source Identification of a Harbor
Spill by Forensic Fingerprinting of Biomarkers .... 134
3.4.5.1 Product Type-Screening ................... 134
3.4.5.2 Characterization of Bicyclic
Sesquiterpanes ........................... 135
3.4.5.3 Confirmation of Source Identification
by Quantitative Evaluation of Alkylated
PAHs and Pentacyclic Terpanes and
Steranes ................................. 135
3.5 Conclusions .............................................. 138
References ............................................... 140
4 Characterization of Polycyclic Aromatic Sulfur
Heterocycles for Source Identification ................... 147
4.1 Introduction ............................................. 147
4.2 Sulfur Compounds in Crude Oil and Petroleum Products ..... 148
4.3 Influence of Refinery Processes on PASH Patterns ......... 150
4.4 Stability of Polycyclic Aromatic Sulfur Heterocycles in
the Environment .......................................... 152
4.5 Petroleum PASH Analysis Techniques ....................... 155
4.5.1 Selective Detection in Gas Chromatography ......... 156
4.5.1.1 Flame Photometric Detection (FPD) ........ 156
4.5.1.2 Atomic Emission Detection (AED) .......... 157
4.5.1.3 Sulfur Chemiluminescence Detection
(SCD) .................................... 157
4.5.1.4 Mass-Selective Detection (MSD) ........... 157
4.5.2 Class Separation of PAH and PASH .................. 157
4.5.3 Comprehensive Two-Dimensional Gas Chromatography .. 158
4.5.4 Quantification of PASH ............................ 158
4.6 Petroleum PASH Markers in Environmental Forensic
Investigations ........................................... 159
4.6.1 PASHs as Source Markers ........................... 160
4.6.2 PASHs as Weathering Markers ....................... 162
4.7 Conclusions .............................................. 164
References ............................................... 164
5 Oil Spill Identification by Comprehensive Two-
Dimensional Gas Chromatography (GC × GC) ................. 169
5.1 Introduction ............................................. 169
5.1.1 The Need for High-Resolution Separations .......... 169
5.1.2 Multidimensional Methods .......................... 170
5.2 Comprehensive Two-Dimensional Gas Chromatography (GC x
GC) ...................................................... 171
5.2.1 Modulation Techniques ............................. 172
5.2.2 Detectors ......................................... 172
5.2.3 Data Processing ................................... 173
5.2.4 GC × GC Chromatogram .............................. 174
5.2.5 Peak Identity and Chromatogram Structure .......... 175
5.2.6 GC × GC Petroleum Applications .................... 180
5.3 Applications of GC × GC to Fingerprint Oil Spills ........ 181
5.3.1 Mobile Bay Marine Diesel Fuel Spill ............... 181
5.3.2 West Falmouth No. 2 Fuel Oil Spill ................ 184
5.3.3 Winsor Cove No. 2 Fuel Oil Spill .................. 187
5.3.4 Buzzards Bay No. 6 (Bunker C) Spill ............... 191
5.3.5 Oil Seeps, Santa Barbara, CA, USA ................. 196
5.4 Conclusion ............................................... 201
Acknowledgments .......................................... 202
References ............................................... 202
6 Application of Stable Isotope Ratios in Spilled Oil
Identification ........................................... 207
6.1 Introduction ............................................. 207
6.2 Isotope Ratios and Their Measurement ..................... 207
6.3 Bulk Isotope Ratios ...................................... 210
6.4 Compound-Specific Isotope Analysis (CSIA) ................ 214
6.4.1 Experimental Considerations ....................... 220
6.5 Weathering ............................................... 220
6.6 Other Isotopes ........................................... 224
6.7 Conclusions .............................................. 224
References ............................................... 225
7 Emerging CEN Methodology for Oil Spill Identification ... 229
7.1 Introduction ............................................. 230
7.2 Scope of the CEN Methodology ............................. 231
7.3 Strategy for Identifying Oil Spills ...................... 231
7.4 Tiered Levels of Analysis and Data Treatment ............. 233
7.4.1 Decision Chart for Identifying Oil Spills ......... 233
7.4.2 Visual Characterization and Preparation/Cleanup
of Oil Samples .................................... 233
7.4.3 Level 1 — GC/FID Screening ........................ 235
7.4.3.1 Evaluation of Weathering ................. 236
7.4.4 Level 2 — GC/MS Fingerprinting .................... 237
7.4.4.1 Diagnostic Ratios from GC/MS
Fingerprinting ........................... 237
7.4.4.2 Diagnostic Ratios Derived from
Alkylated Polycyclic Aromatic Compounds .. 238
7.4.4.3 Diagnostic Ratios Derived from
Petroleum Biomarkers ..................... 239
7.4.4.4 Optional Diagnostic Ratios Derived from
Sesquiterpanes ........................... 240
7.4.5 Level 3 — Treatment of Results .................... 245
7.4.5.1 Comparison of Oil Samples Using
Diagnostic Ratios ........................ 245
7.4.5.2 Criteria for Selecting, Eliminating,
and Evaluating Diagnostic Ratios ......... 245
7.4.5.3 Repeatability Limit and Critical
Difference ............................... 246
7.4.5.4 Elimination of Diagnostic Ratios Using
Signal-to-Noise (S/N) Test ............... 246
7.4.5.5 Elimination of Diagnostic Ratios Using
Duplicate Analyses ....................... 248
7.4.5.6 Optional Comparison of Diagnostic
Ratios Using Multivariate Statistics ..... 249
7.4.6 Final Evaluation and Conclusions .................. 250
7.5 The CEN Methodology in Practice: A Case Study ............ 251
7.5.1 The Spill Case .................................... 251
7.5.2 GC/FID Screening .................................. 251
7.5.3 GC/MS Fingerprinting .............................. 251
7.5.4 Evaluation and Comparison of Diagnostic Ratios .... 251
7.6 Summary .................................................. 254
Acknowledgment ........................................... 255
References ............................................... 255
8 Advantages of Quantitative Chemical Fingerprinting in
Oil Spill Source Identification .......................... 257
8.1 Introduction ............................................. 257
8.2 Qualitative Fingerprinting Methods ....................... 258
8.2.1 Shortcomings of Qualitative Fingerprinting ........ 260
8.2.1.1 Weathered Oils ........................... 260
8.2.1.2 Genetically Similar Oils ................. 260
8.2.1.3 Qualitatively Similar Oils ............... 261
8.2.1.4 Mixing ................................... 261
8.3 Quantitative Fingerprinting Methods ...................... 263
8.3.1 Semiquantitative versus Fully Quantitative
Methods ........................................... 263
8.3.2 Data Generation for Fully Quantitative
Fingerprinting .................................... 265
8.3.2.1 Sample Collection ........................ 265
8.3.2.2 Sample Preparation ....................... 266
8.3.2.3 GC/FID Analysis .......................... 266
8.3.2.4 GC/MS Analysis ........................... 268
8.3.2.5 Data Quality ............................. 269
8.3.3 Selection of Diagnostic Indices ................... 269
8.3.4 Source Identification Protocols for Quantitative
Fingerprinting Data ............................... 272
8.4 Unraveling Mixed Source Oils Using Quantitative
Fingerprinting Data ...................................... 276
8.4.1 Two-Component Mixing Models ....................... 276
8.4.2 Case Study 1 ...................................... 277
8.4.3 Case Study 2 ...................................... 279
8.4.3.1 Mixing Model Case Study 2 ................ 284
8.5 Summary .................................................. 289
References ............................................... 290
9 A Multivariate Approach to Oil Hydrocarbon
Fingerprinting and Spill Source Identification ........... 293
9.1 Introduction ............................................. 293
9.1.1 Multivariate Methods and Oil Fingerprinting ....... 294
9.1.2 Integrated Multivariate Oil Fingerprinting
(IMOF) ............................................ 296
9.2 Sample Preparation and Chemical Analysis ................. 297
9.2.1 Sample Preparation ................................ 297
9.2.2 Analytical Methods ................................ 298
9.2.3 Fluorescence Spectroscopy ......................... 298
9.2.4 GC-MS ............................................. 299
9.2.5 Quality Assurance and Quality Control (QA/QC) ..... 301
9.3 Data Preprocessing ....................................... 302
9.3.1 Partial GC-MS/SIM Chromatograms ................... 303
9.3.1.1 Baseline Removal ......................... 303
9.3.1.2 Retention Time Alignment ................. 304
9.3.1.3 Normalization ............................ 306
9.3.2 Diagnostic Ratios ................................. 306
9.3.3 Preprocessing of Fluorescence Spectra ............. 307
9.4 Multivariate Statistical Data Analysis ................... 308
9.4.1 Multilinear Models ................................ 310
9.4.1.1 Two-Way Case ............................. 310
9.4.1.2 Higher-Order Arrays ...................... 311
9.4.2 Variable Selection and Scaling .................... 312
9.5 Data Evaluation .......................................... 314
9.5.1 Visual Inspection of Score and Loading Plots ...... 315
9.5.2 Numerical Comparisons and Statistical Tests ....... 317
9.6 Conclusions and Perspectives ............................. 319
Acknowledgments .......................................... 321
References ............................................... 322
10 Chemical Heterogeneity of Modern Marine Residual Fuel
Oils ..................................................... 327
10.1 Introduction ............................................. 327
10.1.1 Historical Perspective ............................ 328
10.1.2 Production of Heavy Fuel Oils ..................... 328
10.1.3 Marine Fuel Nomenclature and Classification ....... 329
10.2 Forensic Chemistry Considerations ........................ 330
10.2.1 General Chemical Fingerprinting ................... 330
10.2.2 Samples and Analytical Methods .................... 332
10.3 General Features of Modern Residual Marine Fuel Oils ..... 332
10.4 Molecular Variability among Modern Residual Fuel Oils .... 336
10.4.1 Petroleum Biomarkers .............................. 336
10.4.2 Polycyclic Aromatic Hydrocarbons .................. 338
10.5 Distinguishing Heavy Fuel Oils from Crude Oil ............ 343
10.6 Conclusion ............................................... 346
References ............................................... 346
11 Biodegradation of Oil Hydrocarbons and Its Implications
for Source Identification ................................ 349
11.1 Introduction ............................................. 349
11.2 Biochemistry of Petroleum Biodegradation ................. 349
11.2.1 Aerobic Biodegradation of Hydrocarbons ............ 351
11.2.2 Anaerobic Biodegradation of Hydrocarbons .......... 355
11.3 Subsurface Biodegradation of Petroleum ................... 357
11.3.1 The Biodegradation of Hopanes and the Formation
of 25-Norhopanes .................................. 360
11.4 Factors Limiting Biodegradation .......................... 362
11.5 Microbial Ecology of Petroleum Biodegradation ............ 365
11.5.1 The Succession of Microbial Communities ........... 365
11.5.2 Deep Subsurface Ecology ........................... 367
11.5.2.1 Aerobic Respiration ...................... 367
11.5.2.2 Anaerobic Respiration .................... 368
11.6 Conclusions; Implications of Biodegradation on
Identification ........................................... 369
References ............................................... 370
12 Identification of Hydrocarbons in Biological Samples
for Source Determination ................................. 381
12.1 Introduction ............................................. 381
12.2 Determination of the Primary Route of Hydrocarbon
Accumulation by Biota .................................... 382
12.3 Catabolic Degradation of Hydrocarbons Accumulated by
Biota .................................................... 387
12.3.1 Catabolic Degradation of PAH ...................... 387
12.3.2 Effects of Catabolism on PAH Accumulation,
Persistence, and Depuration ....................... 390
12.4 Modes of Toxic Action of Accumulated Hydrocarbons ........ 393
12.5 Case Study: The Exxon Valdez Oil Spill ................... 396
12.6 Summary .................................................. 398
References ............................................... 398
13 Trajectory Modeling of Marine Oil Spills ................. 405
13.1 Introduction ............................................. 405
13.2 Forecasting and Hindcasting Oil Spill Movement ........... 406
13.3 Oil Spill Transport ...................................... 407
13.3.1 Wind .............................................. 409
13.3.2 Currents .......................................... 411
13.3.3 Turbulent Diffusion ............................... 413
13.4 Evolution of an Oil Spill ................................ 413
13.4.1 Spreading ......................................... 413
13.4.2 Oil Weathering .................................... 414
13.5 Conclusions and Challenges ............................... 416
Acknowledgments .......................................... 416
References ............................................... 416
14 Oil Spill Remote Sensing: A Forensic Approach ............ 419
14.1 Introduction ............................................. 419
14.2 Visible Indications of Oil ............................... 420
14.3 Optical Sensors .......................................... 420
14.3.1 Visible ........................................... 420
14.3.2 Infrared .......................................... 422
14.3.3 Ultraviolet ....................................... 423
14.3.4 Night Vision Cameras .............................. 423
14.4 Laser Fluorosensors ...................................... 423
14.5 Microwave Sensors ........................................ 426
14.5.1 Radiometers ....................................... 426
14.5.2 Radar ............................................. 426
14.5.3 Microwave Scatterometers .......................... 428
14.6 Determination of Slick Thickness ......................... 428
14.6.1 Visual Thickness Indications ...................... 428
14.6.2 Theoretical Approaches ............................ 429
14.6.3 Literature Review of Visual Indications of Oil
Slick Thickness ................................... 429
14.6.4 Oil Slick-Thickness Relationships in Remote
Sensors ........................................... 431
14.6.5 Specific Oil-Thickness Sensors .................... 432
14.7 Acoustic Systems ......................................... 435
14.8 Satellite Remote Sensing ................................. 435
14.9 Detection of Oil under Ice ............................... 436
14.10 Real-Time Displays and Printers ......................... 438
14.11 Future Trends ........................................... 438
References ............................................... 439
15 Advances in Forensic Techniques for Petroleum
Hydrocarbons: The Exxon Valdez Experience ................ 449
15.1 Introduction ............................................. 449
15.2 Identification of Hydrocarbon Sources in PWS ............. 450
15.2.1 Multiple Sources of Hydrocarbons .................. 450
15.2.2 Petrogenic Hydrocarbons ........................... 451
15.2.3 Biogenic Hydrocarbons ............................. 453
15.2.4 Pyrogenic Hydrocarbons ............................ 453
15.3 Composition of Exxon Valdez Crude and Its Weathering
Products ................................................. 453
15.3.1 Bulk Composition and Trace Chemistry .............. 453
15.3.2 Weathering Trends ................................. 457
15.3.2.1 Data Sources ............................. 457
15.3.2.2 Major Fraction Trends .................... 457
15.3.2.3 PAH Trends ............................... 457
15.3.3.1 Mass Loss during Weathering .............. 458
15.4 Resolution of Inputs to the Natural Background ........... 458
15.5 Hydrocarbon Source Allocations ........................... 462
15.5.1 Source Allocation Models .......................... 462
15.5.2 Qualitative Allocation Models ..................... 464
15.5.3 Quantitative Models ............................... 464
15.5.3.1 PAH Ratios ............................... 464
15.5.3.2 Statistical Models ....................... 465
15.5.3.3 Statistical Models ....................... 466
15.5.3.3.1 Multivariate Methods —
Constrained Least Squares ..... 466
15.5.3.3.2 Multivariate Analysis —
Partial Least Squares ......... 468
15.5.3.4 Total Organic Carbon (TOC) Constraints
on Source Allocations .................... 468
15.6 Allocation of Anthropogenic Sources of PAH ............... 469
15.7 Identification of Hydrocarbons in Biological Samples ..... 470
15.8 Applications of Forensic Methods to Assessments of Oil
Bioavailability .......................................... 477
15.8.1 PAH Uptake in Biota ............................... 477
15.8.2 Passive Sampling of PAH in Water .................. 481
15.8.3 Biological Markers ................................ 481
15.9 Summary .................................................. 482
List of Figures .......................................... xxi
Acknowledgments .......................................... 483
References ............................................... 483
16 Case Study: Oil Spills in the Strait of Malacca,
Malaysia ................................................. 489
16.1 Strait of Malacca, Malaysia: Introduction ................ 489
16.1.1 Hydro-Oceanographic Condition of the Strait ....... 489
16.1.2 Ship Traffic in the Strait of Malacca:
Historical and Present ............................ 491
16.2 Chronic and Acute Oil Spill Events in the Strait ......... 491
16.2.1 Contribution of Oil Pollution Sources in
Malaysia ......................................... 491
16.3 Methodology .............................................. 492
16.3.1 Sample Collection ................................. 492
16.3.2 Source Petroleum .................................. 492
16.3.3 Таr-Ball Samples .................................. 492
16.3.4 Sediment Samples .................................. 492
16.3.5 Street Dust Samples ............................... 493
16.3.6 Asphalt Samples ................................... 494
16.3.7 Fresh Crankcase Oil ............................... 494
16.3.8 Used Crankcase Oil ................................ 495
16.3.9 Automobile Tire Rubber ............................ 495
16.3.10 Aerosol Samples .................................. 495
16.4 Analytical Procedure ..................................... 495
16.4.1 Chemicals ......................................... 495
16.4.2 Extraction and Fractionation ...................... 496
16.5 Instrumental Analysis .................................... 496
16.5.1 Analysis of Alkanes and Hopanes ................... 496
16.5.2 N-Cyclohexyl-2-Benzothiozolamine (NCBA) ........... 497
16.5.3 Analysis of PAHs .................................. 497
16.6 Establishment and Application of Biomarker Analysis for
Source Identification of Oil Pollution Sources in the
Strait of Malacca ....................................... 498
16.7 Case Study 1: Development of the Analytical Method for
Oil Pollution Source Identification Using Biomarkers in
the Strait of Malacca .................................... 498
16.7.1 Weathering of Tar Balls .......................... 499
16.8 The Application of Molecular Markers for Source
Identification of Таг-Ball Pollution in Malaysia ......... 501
16.9 Case Study 2: Distribution and Sources of PolyCyclic
Aromatic Hydrocarbons (PAHs) in Rivers and Estuaries in
Malaysia ................................................. 502
16.10 Conclusions and Future Scenario ......................... 502
References ............................................... 503
17 Evaluation of Hydrocarbon Sources in Guanabara Bay,
Brazil ................................................... 505
17.1 Guanabara Bay and Hydrocarbon Apportioning ............... 505
17.1.1 Regional Setting .................................. 506
17.1.2 January 2000 Heavy Fuel Oil Spill ................. 506
17.2 Methodology for Hydrocarbon Determination and Source
Evaluation ............................................... 507
17.2.1 Sampling Design ................................... 507
17.2.2 Chemical Analysis ................................. 508
17.2.2.1 Sediment Sample Extraction ............... 508
17.2.2.2 Extract Cleanup .......................... 509
17.2.2.3 PAH Analysis of Sediment Samples ......... 509
17.2.2.4 Biomarkers ............................... 510
17.2.3 Source Identification Techniques ................. 510
17.2.3.1 PAH Diagnostic Ratios .................... 510
17.2.3.2 PAH Multivariate Statistical Analysis .... 511
17.2.3.3 Biomarker Diagnostic Ratios .............. 511
17.3 Hydrocarbon Results for Guanabara Bay Sediments .......... 511
17.3.1 PAH Quantification and Distribution ............... 511
17.3.2 Hydrocarbon Source Identification ................. 514
17.3.2.1 PAH Diagnostic Ratios .................... 514
17.3.2.2 PAH Principal Component Analysis ......... 525
17.3.2.3 Biomarker Diagnostic Ratios .............. 527
17.4 Conclusions .............................................. 531
Acknowledgments .......................................... 533
References ............................................... 534
Index ......................................................... 537
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