List of Case Studies xiii
List of Boxes xiv
Preface xvi
New in the Second Edition xviii
About the Author xxi
Whom This Book Is Written For xxii
To the Instructor xxiii
Acknowledgments xxiv
List of Symbols xxvi
1 Introduction to Environmental Data Acquisition 1
1.1 Introduction 2
1.1.1 Importance of Scientifically Reliable and Legally Defensible Data 3
1.1.2 Sampling Error vs. Analytical Error During Data Acquisition 4
1.2 Environmental Sampling 9
1.2.1 Scope of Environmental Sampling 9
1.2.2 Where, When, What, How, and How Many 9
1.3 Environmental Analysis 9
1.3.1 Uniqueness of Modern Environmental Analysis 10
1.3.2 Classical and Modern Analytical and Monitoring Techniques 11
Chapter Themes 13
References 13
Questions 14
Problems 15
2 Basics of Analytical and Organic Chemistry 16
2.1 Basic Concepts from Analytical Chemistry 17
2.1.1 Concentration Units 17
2.1.2 Analytical Precision, Accuracy, and Recovery 21
2.1.3 Detection Limit and Quantitation Limit 23
2.1.4 Standard Solution and Standard Calibration Curve 25
2.2 Basic Concepts from Organic Chemistry 27
2.2.1 Types of Organic Functional Groups 28
2.2.2 Important Environmental Organic Pollutants 32
2.2.3 Physical Properties Relevant to Environmental Analysis 43
2.2.4 Regulations Governing the Analysis of Environmental Pollutants 45
Chapter Themes 47
References 48
Questions 49
Problems 51
3 Basics of Environmental Data Validation and Analysis 55
3.1 Measurements of Central Tendency and Dispersion 56
3.2 Understanding Probability Distributions 59
3.2.1 Normal (Gaussian) Distribution and Probability 59
3.2.2 Student’s t Distribution and Confidence Interval 61
3.2.3 F-distribution and Analysis of Variance 63
3.2.4 Nonparametric Tests When Normality Is Not Satisfied 64
3.3 Hypothesis Testing and Type I and II Errors 65
3.4 Detection of Outliers 67
3.4.1 z-test 67
3.4.2 Grubbs’s Test 67
3.4.3 Dixon’s Test 68
3.5 Analysis of Censored Data 72
3.6 Analysis of Spatial and Time Series Data 77
Chapter Themes 80
References 81
Questions 82
Problems 83
4 Environmental Sampling Design 87
4.1 Planning and Sampling Protocols 88
4.1.1 Data Quality Objectives 88
4.1.2 Basic Considerations of Sampling Plan 90
4.2 Sampling Environmental Population 91
4.2.1 Where (Space) and When (Time) to Sample 91
4.2.2 Obtain Representative Samples from Various Matrices 92
4.3 Environmental Sampling Approaches: Where and When 95
4.3.1 Non-Statistically Based Haphazard and Judgmental Sampling 95
4.3.2 Simple Random Sampling 96
4.3.3 Stratified Random Sampling 97
4.3.4 Systematic Sampling 100
4.3.5 Composite Sampling 103
4.3.6 Incremental Sampling 103
4.3.7 Line and Point Transect Sampling 104
4.4 Estimating Sample Numbers and Sampling Frequencies 108
4.4.1 How Many Samples Are Needed 108
4.4.2 How Frequent Samples Are Collected 110
Chapter Themes 112
References 113
Questions 115
Problems 116
5 Environmental Sampling Techniques 120
5.1 General Guidelines of Environmental Sampling Techniques 121
5.1.1 Sequence of Sampling Matrices and Analytes 121
5.1.2 Sample Amount 121
5.1.3 Sample Preservation and Storage 123
5.1.4 Selection of Sample Containers 126
5.1.5 Selection of Sampling Equipment 127
5.2 Grab Sampling Techniques for Various Media: Practical Approaches and Tips 136
5.2.1 Surface Water and Wastewater Sampling 136
5.2.2 Groundwater Sampling 138
5.2.3 Soil and Sediment Sampling 143
5.2.4 Hazardous Waste Sampling 145
5.2.5 Biological Sampling 146
5.2.6 Air and Stack Emission Sampling 146
5.3 Time-Integrated Sampling and Sensing Techniques 148
5.3.1 Passive Samplers 148
5.3.2 Automated Samplers 152
5.3.3 In Situ Sensors 153
5.3.4 Remote Sensing 153
Chapter Themes 153
References 154
Questions 156
Problems 158
6 Methodology and Quality Assurance/Quality Control of Environmental Analysis 159
6.1 Overview on Standard Methodologies 160
6.1.1 The US EPA Methods for Air, Water, Wastewater, and Hazardous Waste 160
6.1.2 Other Applicable Methods: APHA/ASTM/ OSHA/NIOSH/USGS/AOAC 164
6.1.3 An Overview of Methodologies in Other Countries 168
6.2 Selection of Standard Methods 169
6.2.1 Methods for Sample Preparation 170
6.2.2 Methods for Physical, Biological, and General Chemical Parameters 171
6.2.3 Methods for Volatile Organic Compounds 172
6.2.4 Methods for Semivolatile Organic Compounds 173
6.2.5 Methods for Other Contaminants of Emerging Concerns 173
6.3 Field Quality Assurance/Quality Control 175
6.3.1 Types of Field QA/QC Samples 175
6.3.2 Numbers of Field QA/QC Samples 177
6.4 Analytical Quality Assurance/Quality Control 177
6.4.1 Quality Control Procedures for Sample Preparation 177
6.4.2 Quality Control Procedures During Analysis 179
Chapter Themes 185
References 186
Questions 187
Problems 189
7 Wet Chemical and Field Methods for Common Environmental Parameters 191
7.1 Basic Operations in Environmental Laboratories 192
7.1.1 Labware Cleaning Protocols for Trace Analysis 192
7.1.2 Chemical Reagent Purity, Standard, and Reference Materials 193
7.1.3 Volumetric Glassware and Calibration 196
7.1.4 Laboratory Health, Safety, and Emergency First Aid 198
7.1.5 Waste Handling and Disposal 199
7.2 Wet Chemical Methods and Common Techniques in Environmental Analysis 200
7.2.1 Gravimetric and Volumetric Wet Chemical Methods 200
7.2.2 Common Laboratory Techniques 201
7.3 Analytical Principles for Common Wet Chemical Methods 204
7.3.1 Moisture in Solid and Biological Samples 204
7.3.2 Solids in Water, Wastewater, and Sludge: TS, TSS, TDS, TVS 205
7.3.3 Acidity, Alkalinity, and Hardness of Waters 208
7.3.4 Oxygen Demand in Water and Wastewater: DO, BOD, and COD 211
7.3.5 Oil and Grease in Water and Wastewater 216
7.3.6 Residual Chlorine and Chloride in Drinking Water 216
7.3.7 Ammonia in Wastewater 219
7.3.8 Cyanide in Water, Wastewater, and Soil Extract 220
7.3.9 Sulfide in Water and Waste 220
7.4 Field Monitoring Testing Kits and Sensors 221
7.4.1 Field Monitoring of Water Quality Parameters 221
7.4.2 Field Monitoring of Ambient Air Quality 222
7.4.3 Field Monitoring of Soil Quality 223
Chapter Themes 224
References 224
Questions 225
Problems 226
8 Fundamentals of Sample Preparation for Environmental Analysis 229
8.1 Overview of Sample Preparation 230
8.1.1 Purpose of Sample Preparation 230
8.1.2 Overview and Recent Development of Sample Preparation 231
8.2 Sample Preparation for Metal Analysis 233
8.2.1 Total Metals and Metals in Various Species 233
8.2.2 Digestion Methods for Total Metal Analysis 234
8.2.3 Speciation of Metals in Water, Soil, and Sediment 237
8.3 Extraction for SVOC and Non-VOC from Liquid or Solid Samples 240
8.3.1 Separatory Funnel and Continuous Liquid-Liquid Extraction (LLE) 240
8.3.2 Soxhlet and Automatic Soxhlet Extraction (Soxtec) 244
8.3.3 Solid Phase Extraction 244
8.3.4 Solid Phase Microextraction and Stir-Bar Sorptive Extraction 245
8.3.5 Ultrasonic Extraction and Microwave-Assisted Extraction 247
8.3.6 Pressured Fluid Extraction 248
8.3.7 Supercritical Fluid Extraction 248
8.3.8 Comparison and Selection of Organic Extraction Methods 249
8.4 Sample Preparation for VOC in Liquid and Solid Samples 251
8.4.1 Dynamic Headspace Extraction (Purge-and-Trap) 251
8.4.2 Static Headspace Extraction 252
8.4.3 Azeotropic and Vacuum Distillation 253
8.5 Post-Extraction Cleanup of Organic Compounds 255
8.5.1 Theories and Operation Principles of Various Cleanup Methods 255
8.5.2 Recommended Cleanup Method for Selected Compounds 256
8.6 Derivatization for GC and HPLC Analysis 257
Chapter Themes 260
References 260
Questions 262
Problems 263
9 Molecular Spectroscopic Methods in Environmental Analysis 264
9.1 An Introduction to Molecular Spectroscopy 265
9.1.1 Understanding the Interactions of Various Radiations with Matter 265
9.1.2 Use of UV-Visible/Infrared Absorption Spectra for Qualitative Analysis 267
9.1.3 Use of Beer-Lambert’s Law for Quantitative Analysis 268
9.2 UV-Visible Spectroscopy 271
9.2.1 Principles of UV-Visible Spectroscopy 272
9.2.2 UV-Visible Instrumentation 281
9.2.3 UV-Visible as a Workhorse in Environmental Analysis 282
9.2.4 Practical Aspects of UV-Visible Spectrometry 284
9.3 Infrared Spectroscopy 286
9.3.1 Principles of Infrared Spectroscopy 286
9.3.2 Instruments of Infrared Spectroscopy 292
9.3.3 Applications in Industrial Hygiene and Air Pollution Monitoring 294
9.3.4 Sample Preparations for Infrared Spectroscopic Analysis 296
9.4 Raman Spectrometry 296
9.5 Photoluminescence and Chemiluminescence 299
Chapter Themes 300
References 301
Questions 302
Problems 305
10 Atomic Spectroscopy for Metal Analysis 306
10.1 Introduction to the Principles of Atomic Spectroscopy 307
10.1.1 Flame and Flameless Atomic Absorption 307
10.1.2 Inductively Coupled Plasma Atomic Emission 310
10.1.3 Atomic X-ray Fluorescence 312
10.2 Instruments for Atomic Spectroscopy 313
10.2.1 Flame and Flameless Atomic Absorption Spectroscopy 313
10.2.2 Cold Vapor and Hydride Generation Atomic Absorption 315
10.2.3 Inductively Coupled Plasma Atomic Emission 318
10.2.4 Atomic X-ray Fluorescence 319
10.3 Selection of the Proper Atomic Spectroscopic Techniques 320
10.3.1 Comparison of Detection Limits and Working Range 320
10.3.2 Comparison of Interferences 320
10.3.3 Other Considerations 323
10.4 Speciation of Metals in Environmental Samples 325
10.5 Practical Tips to Metal Analysis 326
10.5.1 Sample Digestion and Pretreatment 326
10.5.2 Instrumental Drift and Run Sequence QA/QC 327
10.5.3 Erroneous Data and Methods of Calibrations 327
10.5.4 Results Calculation and Reporting 330
Chapter Themes 331
References 332
Questions 333
Problems 335
11 Chromatographic Methods for Environmental Analysis 336
11.1 Introduction to Chromatography 337
11.1.1 Types of Chromatography and Separation Columns 337
11.1.2 Common Stationary Phases: The Key to Separation 339
11.1.3 Column Dimensions and Packing 346
11.1.4 Operational Parameters for Compound Separation 348
11.1.5 Terms and Theories of Chromatogram 352
11.1.6 Use of Chromatograms for Qualitative and Quantitative Analysis 356
11.2 Instruments of Chromatographic Methods 356
11.2.1 Gas Chromatography 357
11.2.2 High Performance Liquid Chromatography 358
11.2.3 Ion Chromatography 360
11.2.4 Supercritical Fluid Chromatography 362
11.3 Common Detectors for Chromatography 363
11.3.1 Detectors for Gas Chromatography 363
11.3.2 Detectors for High Performance Liquid Chromatography 368
11.3.3 Detectors for Ion Chromatography 370
11.4 Applications of Chromatographic Methods in Environmental Analysis 371
11.4.1 Gases, Volatile, and Semivolatile Organics with GC 372
11.4.2 Semivolatile and Nonvolatile Organics with HPLC 373
11.4.3 Ionic Species with Ion Chromatography 374
11.5 Practical Tips to Chromatographic Methods 375
11.5.1 What Can and Cannot Be Done with GC and HPLC 375
11.5.2 Development for GC and HPLC Methods 375
11.5.3 Overview on Maintenance and Troubleshooting 376
Chapter Themes 379
References 380
Questions 381
Problems 383
12 Electrochemical Methods for Environmental Analysis 385
12.1 Introduction to Electrochemical Theories 386
12.1.1 Review of Redox Chemistry and Electrochemical Cells 386
12.1.2 General Principles of Electroanalytical Methods 390
12.1.3 Types of Electrodes and Notations for Electrochemical Cells 394
12.2 Potentiometric Applications in Environmental Analysis 395
12.2.1 Measurement of pH 396
12.2.2 Measurement of Ions by Ion Selective Electrodes (ISEs) 398
12.2.3 Potentiometric Titration (Indirect Potentiometry) 400
12.3 Voltammetric Applications in Environmental Analysis 401
12.3.1 Measurement of Dissolved Oxygen 401
12.3.2 Measurement of Anions by Amperometric Titration 403
12.3.3 Measurement of Metals by Anodic Stripping Voltammetry (ASV) 404
Chapter Themes 406
References 407
Questions 408
Problems 410
13 Mass Spectrometry in Environmental Analysis 411
13.1 Basics of Mass Spectrometry 412
13.1.1 Atomic and Molecular Mass in Mass Spectrometry 412
13.1.2 Basic Components of Mass Spectrometers 415
13.2 Ionization Techniques 417
13.2.1 Hard Ionization: Electron Ionization 417
13.2.2 Chemical Ionization 419
13.2.3 Atmospheric Pressure Ionization 420
13.2.4 Matrix-Assisted Laser Desorption Ionization 423
13.2.5 Other Molecular Ionization Methods 424
13.2.6 Atomic Ionization Sources for Inorganic Compounds 426
13.3 Mass Analyzers 428
13.3.1 Quadrupole Analyzers 428
13.3.2 Ion Trap 429
13.3.3 Time-of-Flight Analyzers 430
13.3.4 Magnetic Sector Analyzers 432
13.3.5 Tandem, Sequential, and Hybrid Mass Spectrometry 433
13.4 Hyphenated Mass Spectrometric Methods 435
13.4.1 Hyphenated Atomic Mass Spectrometry (ICP-MS) 436
13.4.2 Hyphenated Gas Chromatography-Mass Spectrometry (GC-MS) 440
13.4.3 Hyphenated Liquid Chromatography-Mass Spectrometry (LC-MS) 441
13.5 Mass Spectra and Molecule Fragmentation 442
13.5.1 Terminologies of Mass Spectrum 443
13.5.2 Isotopic Peaks 444
13.5.3 Fragmentation Patterns 446
13.5.4 Molecular Ions upon Soft Ionization 446
13.6 Mass Spectrometric Applications in Environmental Analysis 448
13.6.1 Targeted Analysis Using Mass Spectrometry 449
13.6.2 Non-Targeted Analysis Using Mass Spectrometry 450
Chapter Themes 451
References 452
Questions 453
Problems 458
14 Other Instrumental Methods in Environmental Analysis 459
14.1 Nuclear Magnetic Resonance (NMR) Spectroscopy 460
14.1.1 Instrument Components of an NMR Spectrometer 460
14.1.2 The Origin of NMR Signals 461
14.1.3 Molecular Structures and 1 H NMR Spectra 464
14.1.4 Molecular Structures and 13 C NMR Spectra 469
14.1.5 Applications of NMR in Environmental Analysis 471
14.2 Surface and Microscopic Characterization 474
14.2.1 An Overview of Various Surface Characterization Techniques 474
14.2.2 X-ray Photoelectron Spectroscopy 475
14.2.3 Auger Electron Spectroscopy 477
14.2.4 Electron Microscopy: SEM and TEM 479
14.2.5 Scanning Probe Microscopes: STM and AFM 481
14.3 Radiochemical Analysis 484
14.3.1 Sources and Properties of Several Important Radionuclides 484
14.3.2 Preservation of Radioactive Samples 486
14.3.3 Measurement of Radioactive Samples 486
14.4 Screening Methods Using Immunoassay 489
Chapter Themes 489
References 490
Questions 491
Problems 494
Appendix A: Common Abbreviations and Acronyms 495
Appendix B1: National Primary Drinking Water Regulations 503
Appendix B2: National Ambient Air Quality Standards 507
Appendix C: Structures and Properties of Important Organic Pollutants 508
Appendix D1: Standard Normal Cumulative Probabilities 519
Appendix D2: Percentiles of Student’s t Distribution 521
Appendix D3: Critical Values for the F-Distribution 523
Appendix E: Required Containers, Preservation Techniques, and Holding Times 526
Appendix F: Answers to Selected Questions and Problems 529
Appendix G: Periodic Table 537
Index 538
