Fundamentals of Environmental Sampling and Analysis

Chunlong (Carl) Zhang, PhD, Professor of Environmental Science at the College of Science and Engineering, University of Houston - Clear Lake, Texas, USA. He is also a registered professional engineer (PE) in the field of environmental engineering, and has published extensively on environmental analysis and contaminant remediation.

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