Fundamentals of Environmental Sampling and Analysis

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