Analytical Techniques in the Oil and Gas Industry for Environmental

Monitoring
Analytical Techniques in the Oil and Gas
Industry for Environmental Monitoring

Edited by
Melissa N. Dunkle
The Netherlands

William L. Winniford
USA
This edition first published 2020
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 v

Contents

Part I Scope 1

1 Introduction 3
Melissa N. Dunkle and William L. Winniford
1.1 Introduction 3
1.1.1 Petroleum Cycle 3
1.1.2 Well-Known Cases of Environmental Contamination 4
1.1.2.1 Oil-Drilling Rig Deepwater Horizon 4
1.1.2.2 Sanchi Oil Tanker Collision 6
1.1.3 Summary 6
1.2 Petroleum 7
1.3 Analytics 9
1.4 Reservoir Tracers 12
1.5 Emissions from the Petroleum Industry 12
1.6 Environmental Analysis and Monitoring 14
1.7 Conclusions 17
References 17

Part II Introduction to the Petroleum Industry 21

2 Petroleum: From Wells to Wheels 23

Clifford C. Walters, Steven W. Levine, and Frank C. Wang
2.1 Introduction 23
2.2 Petroleum in the Ancient World 23
2.3 The Petroleum System 28
2.3.1 Source Rocks 28
vi Contents

2.3.2 Generation of Petroleum 34

2.3.3 Migration and Accumulation 35
2.4 The Upstream 37
2.4.1 Exploration 37
2.4.1.1 Play and Prospect Evaluation 38
2.4.1.2 Predicting Petroleum Quantity and Quality 43
2.4.2 Drilling 45
2.4.2.1 Development of Drilling Technology 46
2.4.2.2 Modern Drilling Practices 49
2.4.2.3 Well Logging 52
2.4.2.4 Development 57
2.4.3 Production 58
2.4.3.1 Primary, Secondary, and Tertiary Production 58
2.4.3.2 Surface Oil Sands 61
2.4.3.3 Unconventional Resources 61
2.4.3.4 Plug and Abandonment 66
2.5 Mid-Stream 67
2.5.1 Transportation 67
2.5.2 Storage 70
2.6 Downstream 72
2.6.1 Evolution of Modern Refining 72
2.6.2 Modern Refinery Processes 73
2.6.2.1 Crude Oil Pretreatment 75
2.6.2.2 Separation 75
2.6.2.3 Conversion 81
2.6.2.4 Purification 95
2.6.2.5 Sweetening and Treating 100
2.6.3 Fuel Products 102
2.6.3.1 Mogas (Motor Gasoline) 103
2.6.3.2 Diesel 104
2.6.3.3 Jet Fuels/Kerosene 106
2.6.3.4 Fuel Oil 106
2.6.3.5 Liquefied Petroleum Gas (LPG) 107
2.7 Petrochemicals 107
2.7.1 Olefins: Prime and Higher Olefins 107
2.7.2 Aromatics 109
2.7.3 Lubes 109
2.7.4 Other Products 110
2.8 The Future of Petroleum 110
References 112
 Contents vii

Part III Analytical Techniques Utilized in the Petroleum

Industry 121

3 Petroleum Analysis Through Conventional Analytical

Techniques 123
Melissa N. Dunkle and William L. Winniford
3.1 Introduction to Petroleum Analysis 123
3.2 Brief History on Petroleum Analysis 123
3.2.1 How Petroleum Analysis Influenced Developments in Gas
Chromatography 124
3.2.1.1 Detector Technology 125
3.2.1.2 Column Technology 132
3.3 Conventional Analysis of Petroleum 135
3.3.1 Distillation 136
3.3.2 PIONA Analyzer 137
3.3.3 Detailed Hydrocarbon Analysis 138
3.3.4 GC-MS Analysis for Unknown and Biomarker Identification 139
3.3.4.1 Diamondoids 140
3.3.4.2 Naphthenic Acids 141
3.3.4.3 Biomarkers 142
3.3.5 Total Petroleum Hydrocarbon (TPH) and Polycyclic Aromatic
Hydrocarbon (PAH) and Their Environmental Impact 145
3.3.6 Tar Analysis 146
3.3.7 Analysis of Heteroatoms and Heavy Metals 149
3.3.7.1 Heteroatoms 149
3.3.7.2 Heavy Metals 150
3.3.8 Additional Analytical Applications for Petroleum 150
References 150

4 Advanced Analytics for the Evaluation of Oil, Natural Gas,

and Shale Oil/Gas 161
Emmie Dumont, Pat Sandra, Kyra A. Murrell, Frank L. Dorman,
Allegra Leghissa, and Kevin A. Schug
4.1 IRMS in the Oil and Gas Industry 161
4.1.1 IRMS: General 161
4.1.1.1 Introduction 161
4.1.1.2 Isotopic Fingerprint 162
4.1.2 IRMS: The Technique 164
4.1.2.1 Introduction 164
4.1.2.2 Ionization 164
4.1.2.3 Mass Analyzer 164
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4.1.2.4 Detection 165

4.1.2.5 Referencing 165
4.1.2.6 Bulk Analysis 165
4.1.3 Compound Specific IRMS 166
4.1.3.1 Introduction 166
4.1.3.2 GC-IRMS 166
4.1.3.3 LC-IRMS 167
4.1.3.4 Two-Dimensional GC-IRMS 168
4.1.4 IRMS Applications in the Oil and Gas Industry 169
4.1.4.1 Introduction 169
4.1.4.2 Oil Fingerprinting 171
4.1.4.3 Air Pollution 172
4.1.4.4 Differentiating Oil Derived Products 174
4.1.4.5 Inherent Tracers for Carbon Capture and Storage (CCS) 174
4.1.5 Conclusions Over Utilization of IRMS in the Oil and Gas
Industry 176
4.2 Advanced Analytics for the Evaluation of Oil, Natural Gas, and Shale
Oil/Gas: Comprehensive GC (GC × GC) 176
4.2.1 Background 176
4.2.2 Basic Principles of GC × GC: Instrumentation 178
4.2.3 Basic Principles of GC × GC: Columns 180
4.2.4 Basic Principles of GC × GC: Modulators 184
4.2.5 Basic Principles of GC × GC: Detectors 186
4.2.6 Basic Principles of GC × GC: Data Processing 187
4.2.7 Petrochemical Applications: Group-Type Analysis 190
4.2.8 Petrochemical Applications: Contaminated Soil and Sediments 193
4.2.9 Petrochemical Applications: Marine Oil Spills 196
4.2.10 Petrochemical Applications: Hydraulic Fracturing 199
4.2.11 Conclusions of Utilizing GC × GC in the Oil and Gas Industry 201
4.3 Petroleum and Hydrocarbon Analysis by Gas Chromatography:
Vacuum Ultraviolet Spectroscopy 202
4.3.1 Introduction to GC-VUV 202
4.3.2 GC-VUV Data Processing 204
4.3.2.1 Time Interval Deconvolution (TID) Algorithm 206
4.3.2.2 Pseudo-absolute Quantitation 208
4.3.3 GC-VUV Applications 210
4.3.4 GC-VUV Conclusions 214
References 215
 Contents ix

5 Liquid Chromatography: Applications for the Oil and Gas

Industry 225
Denice van Herwerden, Bob W. J. Pirok, and Peter J. Schoenmakers
5.1 Introduction 225
5.1.1 Petroleum Industry 225
5.1.2 Introduction to Liquid Chromatography 226
5.2 Group-Type Separations 228
5.2.1 Group-Type Separations of Heavy Distillates 228
5.2.2 Other Group-Type Separations 232
5.3 Molecular-Weight Distribution 233
5.4 Target Analysis 236
5.4.1 Polyaromatic Hydrocarbons 236
5.4.2 Naphthenic Acids 240
5.4.3 Phenols 244
5.5 LC as a Pre-separation Technique for GC Analysis 245
5.6 Conclusions 247
References 248

6 Supercritical Fluids in Chromatography: Applications to the

Oil and Gas Industry 259
Didier Thiébaut and Robert M. Campbell
6.1 Introduction 259
6.2 Basics of SFC 260
6.2.1 Packed Column SFC 262
6.2.1.1 Implementation 262
6.2.1.2 Applications of Packed Column SFC 264
6.2.2 Capillary SFC 265
6.3 Simulated Distillation (SIMDIST) 266
6.3.1 Experimental 267
6.3.2 Results 267
6.4 Group-Type and Related Separations 270
6.4.1 Heavy Samples 271
6.4.2 Additives 272
6.5 Detailed Separations 273
6.5.1 Surfactant and Alkoxylate Polymer Analysis by SFC 273
6.5.1.1 Open Tubular Columns 273
6.5.1.2 Packed Capillary Column SFC of Surfactants 274
6.5.2 Packed Column SFC of Surfactants 275
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6.5.2.1 Surfactants by Sub-2 μm Particle Packed Column SFC 276

6.5.2.2 Surfactant Characterization by SFC/MS: Software-Assisted
Deconvolution of Co-polymers 280
6.5.2.3 CO2 Cloud Point Pressures of Non-ionic Surfactants by Capillary and
Packed Column SFC 280
6.5.2.4 CO2 /Water Partition Coefficients by SFC 280
6.5.2.5 SFC of Ionic Surfactants 281
6.5.3 Capillary SFC of Surfactants 281
6.5.3.1 Large Volume Injection in Capillary SFC 281
6.5.3.2 Splitless Injection in Capillary SFC 282
6.5.4 Separations of Polyaromatic Hydrocarbons (PAHs) 283
6.5.5 SFC in Multidimensional Separations 285
6.5.5.1 LC × SFC 285
6.5.5.2 Feasibility of SFC × SFC 287
References 288

7 Online and In Situ Measurements for Environmental

Applications in Oil and Gas 299
Eric Schmidt, J.D. Tate, William L. Winniford, and Melissa N. Dunkle
7.1 Introduction 299
7.2 Characteristics of On-line Analyzers 300
7.2.1 Zone Classification 300
7.2.2 Sampling Systems 301
7.2.3 Detection 302
7.3 Water Analysis 302
7.3.1 General Water Analysis 302
7.3.2 Application: Benzene in Drinking Water 303
7.4 Air Quality and Emissions Monitoring 304
7.4.1 Regulations 305
7.4.1.1 US Air Monitoring 305
7.4.1.2 European Union Air Monitoring 305
7.4.2 Proton Transfer Reaction Mass Spectrometry for Emission
Monitoring 307
7.5 Sample Conditioning 309
7.6 Well Drilling and Production 309
7.6.1 Well Logging 310
7.6.2 Emissions 312
7.7 Texas Commission on Environmental Quality 312
7.8 Fenceline Monitoring 313
7.9 Pipeline and Fugitive Emission Monitoring with Drones 317
7.10 Types of Continuous Emission Monitors 317
 Contents xi

7.10.1 Nondispersive IR (NDIR) 317

7.10.2 UV and Dispersive IR 319
7.10.3 Chemiluminescent NOx /SOx Analyzers 319
7.10.4 TDL Analyzers 320
7.10.5 QCL Analyzers 321
7.11 Portable GCs 321
References 324

Part IV Special Cases and Examples Related to the

Petroleum Industry 329

8 Tracers for Oil and Gas Reservoirs 331

William L. Winniford and Melissa N. Dunkle
8.1 Introduction 331
8.2 Types of Tracers 334
8.2.1 Radioactive Water Tracers 334
8.2.2 Radioactive Gas Tracers 336
8.2.3 Radioactive Measurement Techniques 336
8.2.4 Example Studies of Radioactive Tracers 338
8.2.5 Chemical Water Tracers 338
8.2.6 Chemical Gas Tracers 339
8.2.7 Naturally Occurring Tracers 340
8.2.7.1 Isotopes 340
8.2.7.2 Biomarkers 341
8.3 Regulations 341
References 343

9 Environmental Impact of Emissions Originating from the

Petroleum Industry 347
Melissa N. Dunkle and William L. Winniford
9.1 Global Warming 347
9.1.1 Causes of Global Warming 347
9.1.2 Combatting Global Warming 349
9.2 Environmental Impact of Diesel Emissions 350
9.2.1 Diesel Engine 350
9.2.2 Diesel Exhaust 350
9.2.3 Diesel Engine Modifications 351
9.2.4 Diesel Fuel Modifications 354
9.2.4.1 Low Sulfur Diesel 355
9.2.4.2 Ultra-Low Sulfur Diesel 355
xii Contents

9.2.4.3 Biodiesel 355

9.2.4.4 Modification of Diesel and Biodiesel with Oxygenates 357
9.2.5 Sulfur Monitoring of Diesel Fuels 358
9.2.6 Monitoring Air Pollution/Haze 359
9.3 Environmental Impact of Fossil Fuel Sourcing and Energy Conversion
on Global Warming 360
9.3.1 Coal Mining, Natural Gas Wells, and Methane Release 360
9.3.1.1 Coal Mine Methane 362
9.3.1.2 Natural Gas Methane 363
9.3.2 Fossil Fuel Power Stations 363
9.3.2.1 Coal-Fired Power Station 363
9.3.2.2 Gas-Fired Power Station 364
9.3.3 Emissions from Fossil Fuel Power Stations 364
9.3.3.1 Carbon Dioxide 365
9.3.3.2 Sulfur Dioxide 366
9.3.3.3 Nitrogen Oxides 367
9.3.3.4 Particulate Matter (PM) 367
9.3.3.5 Coal Ash and Heavy Metals 368
9.3.4 Wastewater from Fossil Fuel Power Stations 369
9.3.5 Analysis of Ground Water 371
References 371

Part V Environmental Analysis 379

10 Environmental Analysis of Soil, Water, and Air 381

Paige Teehan, Kyra A. Murrell, Romano Jaramillo, A. Paige Wicker,
Robert Parette, Kevin A. Schug, and Frank L. Dorman
10.1 Water and Soil Monitoring 381
10.2 Total Petroleum Hydrocarbons in Soil 382
10.2.1 Introduction 382
10.2.2 Soil as a Matrix 383
10.2.3 Sample Preparation 383
10.2.3.1 Collection and Preservation 384
10.2.3.2 Extraction 384
10.2.3.3 Concentration 384
10.2.3.4 Cleanup 384
10.2.4 Sample Analysis 386
10.3 Volatile Organic Compound Analysis 389
10.3.1 Introduction 389
10.3.2 Methane Monitoring 389
 Contents xiii

10.3.2.1 Cavity Ring-Down Laser Spectrometry Techniques 390

10.3.2.2 Mobile Platforms for Bottom-Up Analyses 391
10.3.2.3 Aircraft-Based Top-Down Analysis 392
10.3.3 Non-Methane VOC Monitoring 392
10.3.3.1 Air Sampling 392
10.3.3.2 Analysis of Air Samples 393
10.4 Water Analysis 393
10.4.1 Introduction 393
10.4.2 Sample Preparation 395
10.4.3 Sample Analysis 397
10.5 Portable GCs for Field Monitoring 402
10.5.1 Introduction 402
10.5.2 Analyzing Field Samples 403
10.6 Fingerprinting in the Oil and Gas Industry 404
10.6.1 Introduction 404
10.6.2 Hydrocarbon Fingerprinting 405
10.6.3 Additional Texts on Fingerprinting Oil Spills and Petroleum
Products 405
References 406

Part VI Future Trends in the Petroleum Industry 417

11 Future Trends 419

William L. Winniford and Melissa N. Dunkle
11.1 Introduction 419
11.2 Climate Change 421
11.3 Likely Scenarios 422
11.3.1 Gas Emissions 422
11.3.2 Water Emissions 425
11.3.3 Oil Sands 427
11.3.4 Food Contact – MOSH/MOAH 428
11.3.5 Industry 4.0 and the 4th Wave of Environmentalism 428
11.4 Summary 430
References 430

Index 433