Handbook of environmental analysis : chemical pollutants ...

Handbook of

Environmental AnalysisChemical Pollutants in Air, Water,

Soil, and Solid Wastes

Third Edition

Pradyot Patnaik

CRC Press is an imprint of the

Taylor & Francis Group, an Informa business

Contents

Preface xxvii

Acknowledgments xxix

Author xxxi

SECTION I Analytical Techniques

Chapter 1 Environmental Analysis: An Overview 3

Chapter 2 Precision and Accuracy of Analysis 5

Statistics in Environmental Analysis 5

Quality Assurance and Quality Control in Environmental Analysis 6

Precision and Accuracy 6

Control Charts 13

Chapter 3 Analysis of Organic Pollutants by Gas Chromatography 15

Selection of Column 16

Detectors 18

Calibration 18

Calculations 19

External Standard Calibration 19

Alternative Calculation 20

Internal Standard Method 21

Routine Analysis 21

Chapter 4 Analysis of Organic Pollutants by Gas Chromatography/Mass Spectrometry 23

Terms and Definitions 23

Application of Mass Spectrometry 23

Interpretation of Mass Spectra 24

Number of Carbon Atoms 26

Nitrogen Rule 26

Index of Hydrogen Deficiency 26

Determination of Molecular Formula 26

Chemical Ionization 27

Limitation of GC/MS Analysis 28

U.S. EPA Methods 28

Volatile Organics by Purge and Trap Method 29

Semivolatile Organics 30

Tuning 30

Compound Identification 32

Calibration 32

References 34

viii Contents

Chapter 5 Extraction of Organic Pollutants and Sample Cleanup 35

Sample Extraction 35

Liquid-Liquid Extraction 35

Solid Phase Extraction 36

Soxhlet Extraction 37

Supercritical Fluid Extraction 37

Cleanup 37

Acid-Base Partitioning 38

Alumina Column Cleanup 38

Silica Gel Cleanup 38

Florisil Column Cleanup 39

Gel-Permeation Cleanup 39

Sulfur Cleanup 39

Permanganate-Sulfuric Acid Cleanup 39

Chapter 6 Titrimetric Analysis 41

Acid-Base Titration 41

Calculation 44

Oxidation-Reduction Titrations 46

Standardization of Oxidants 49

Reducing Agent 50

Oxidation-Reduction Indicators 50

Iodometric Titration 51

Role of Potassium Iodide 53

Reducing Agent 54

Standardization of Na2S203 54

Starch Indicator 55

Argentometric Titration 55

Complexometric Titrations 57

Potentiometric Titration 59

End Point Detection 59

Chapter 7 Colorimetric Analysis 63

Chapter 8 Analysis of Metals by Atomic Absorption and Emission Spectroscopy 67

Sample Digestion for Metals 68

Atomic Absorption Spectrometry 68

Chelation-Extraction Method 70

Hydride Generation Method 71

Cold Vapor Method for Mercury Determination 71

Accuracy in Quantitation 72

Standard Addition 72

Atomic Emission Plasma Spectroscopy 72

ICP Mass Spectrometry 74

Chapter 9 Ion-Selective Electrodes Analysis 77

Environmental Sample Analysis 77

Standard Calibration Method 78

Contents ix

Standard Addition Method 79

Sample Addition Method 80

Chapter 10 Application of High-Performance Liquid Chromatography in

Environmental Analysis 81

Chapter 11 Ion Chromatography 85

References 88

Chapter 12 Air Analysis 89

Sampling Plan 89

Air Sampling 90

Direct Collection of Air 90

Use of Adsorbent Tubes 90

Air Sampling for Particulates and Inorganic Substances 91

Flow Rate 91

Chemical Analysis 92

Calculation 92

Chapter 13 Application of Immunoassay Techniques in Environmental Analysis 97

Extraction 98

Calculation 98

Chapter 14 Derivatization Reactions in Trace Chemical Analysis 101

Derivatization Reactions: General Discussion 101

Alkylation 102

Acylation 104

Sylilation 105

Diazotization 106

Selection of Derivatizing Reagent 106

Chapter 15 Microbial Analysis 109

Coliform Groups of Bacteria 109

Sample Collection, Preservation, and Storage 110

MF Method for Testing TCs and E. coli 110

Outline of the Method 110

Interference Ill

Reagents, Standards, and Equipment Ill

Quality Control 112

Procedure 113

Calculations/Data Analysis 113

Multiple Tube Fermentation/MPN Index Test 114

Outline of the Test 114

Procedure 114

Radiometric Detection of Fecal Coliforms 115

Bioluminescence Test 115

Seven-Hour Fecal Coliform Test 115

x Contents

SECTION II Specific Classes of Substances

and Aggregate Properties

Chapter 16 Aldehydes and Ketones 119

Derivatization with 2,4-PNPH 119

Chromatographic Columns and Conditions 122

Sample Collection and Holding Time 122

Air Analysis 122

Chapter 17 Alkalinity 125

Calculation 125

Chapter 18 Bromide 127

Phenol Red Colorimetric Method 127

Procedure 127

Reagents 127

Titrimetric Method 128

Determination of Bromide Plus Iodide 128

Procedure 128

Determination of Iodide 129

Calculation 129

Chapter 19 Chloride 131

Mercuric Nitrate Titrimetric Method 131

Procedure 131

Reagents 132

Argentometric Titrimetric Method 132

Procedure 132

Reagents 133

Automated Ferricyanide Colorimetric Method 133

Procedure 133

Reagents 133

Gravimetric Determination of Chloride 134

Procedure 134

Calculation 134

Chapter 20 Chlorine and Chloramines 135

General Discussion 135

Colorimetric Methods for Chlorine Analysis 136

DPD Colorimetric Test 136

Syringaldazine Colorimetric Test 137

Orthotolidine Colorimetric Test 137

Titrimetric Procedures for Chlorine Analysis 137

DPD Titration Method 137

Iodometric Back Titration Method 139

Chloramines 139

Contents xi

Chapter 21 Cyanate 141

Calculation 141

Procedure 141

Chapter 22 Cyanide, Total 143

Silver Nitrate Titrimetric Method 143

Procedure 143

Reagents 144

Colorimetric Method 144

Procedure 145

Preparation of Cyanide Standards and Calibration Curve 145

Reagents 146

Determination of Cyanide in Soil, Sediment, and Solid Waste 146

Cyanides in Aerosol and Gas 147

Chapter 23 Cyanide Amenable to Chlorination 149

Procedure 149Alternative Procedure 149

Reagents 150

Chapter 24 Emerging Pollutants: Classification, Extractions, and AnalyticalTechniques—An Overview 151

General Definition and Classifications 151

Sample Extractions 151

Analysis 154

Chapter 25 Emerging Pollutants: Nonionic Surfactants—Alkylphenols and

Their Ethoxylates 155

Structures 155

Sample Extractions and Analysis: General Discussion 156

SPE-LC/MS Method (LC Tandem MS [LC-MS/MS]) 158

SPE-GC/MS Method 159

References 160

Chapter 26 Emerging Pollutants: Organophosphate Flame Retardants, Plasticizers,and Lubricants 163

Analysis of Indoor Dust 166References 166

Chapter 27 Emerging Pollutants: Pharmaceuticals and Personal Care Products 167

U.S. EPA Method 1694.. 167

Summary of the Method 167

Sample Preparation 169

Sample Cleanup 173

LC-MS/MS Analysis 173

Qualitative Determination and Quantification 175

xii Contents

Quality Assurance/Quality Control 176

Sample Collection, Preservation, and Holding Time 176

References 177

Chapter 28 Emerging Pollutants: Steroids and Hormones 179

Outline of the Procedure 179


GC Conditions 181

MS Conditions 181

Calibration and Quantitation 181

Quality Control 184

References 184

Chapter 29 Emerging Pollutants: Nanomaterials 185

Classifications and Uses 185

Separation, Characterization, and Detection of Nanoparticles in

Food and Agricultural Samples 185

Environmental Samples 187

Chapter 30 Fluorides 189

Colorimetric SPADNS Method 189

Procedure 189

Automated Colorimetric Method 189

Chapter 31 Haloacetic Acids 191

Alternative Methods 191

References 192

Chapter 32 Halogenated Hydrocarbons 193

Solvent Extraction 194

Sample Collection and Preservation 197

Internal Standards/Surrogates and Tuning Compounds 197

Air Analysis 197

Chapter 33 Hardness 201

Hardness Determinations 201

Calculation 201

Titration 201

Chapter 34 Herbicides: Chlorophenoxy Acid 203

Analysis 203


Hydrolysis 204

Esterification 204

Gas Chromatographic Analysis 206

Air Analysis 206

Contents xiii

Chapter 35 Herbicides: Glyphosate 209

Water Analysis 209

HPLC Method 209

Sampling and Storage 209

Detection Limit 210

Miscellaneous Methods for Analysis of GLYPH Residues in Water,

Soil, Sludge, Fruit, and Vegetable Extracts 210

References 211

Chapter 36 Hydrocarbons 213

Analysis 213

Total Petroleum Hydrocarbons 213

Gasoline Range Organics 214

Diesel Range Organics 214

Chapter 37 Hydrocarbons, Polynuclear Aromatic 217

HPLC Columns and Conditions 217

GC Columns and Conditions 218

MS Conditions 218

Sample Extraction and Cleanup 219

Air Analysis 220

Reference 220

Chapter 38 Nitrogen (Ammonia) 221

Sample Distillation 221

Reagents 222

Titrimetric Method 222

Reagents 222

Colorimetric Nesslerization Method 223

Procedure 223

Calculation 223

Reagents and Standards 224

Colorimetric Phenate Method 224

Procedure 225

Calculation 225


Ion-Selective Electrode 226

Procedure 226


AIR ANALYSIS 227

References 228

Chapter 39 Nitrogen (Nitrate) 229

Cadmium Reduction Method 229

Procedure 230

Apparatus, Reagents, and Standards 230

Miscellaneous Reduction Method 231

xiv Contents

Nitrate Electrode Method 231

Procedure 231

Reagents 231

Chapter 40 Nitrosamines 233

Extraction 234

Analysis 235

Air Analysis 235

References 236

Chapter 41 Oil and Grease 237

Partition-Gravimetry Method 237

Calculation 238

Partition-Infrared Method 238

Solid Phase Partition-Gravimetric Method 239

Hydrocarbons 239

Sample Collection and Preservation 240

References 240

Chapter 42 Oxygen Demand, Biochemical 241

Graphical Calculation 242

Method 242

Measurement of DO 243

Iodometric or Winkler Method 243

Electrode Method 244

Kinetics of BOD Reaction 244

Reference 245

Chapter 43 Oxygen Demand, Chemical 247

Standardization of FAS Titrant 249

Indicator Solution 249

Sample Treatment 249

Colorimetric Analysis 250

Chapter 44 Oxyhalides 251

Analysis of Oxyhalides by U.S. EPA Methods 251

U.S. EPA Method 300.1 251

U.S. EPA Method 317.0 252

Interference 252


Quality Control 253

Miscellaneous Methods 253

References 254

Chapter 45 Pesticides: Carbamate, Urea, and Triazine 255

Carbamate Pesticides 255

Contents xv

LC Columns 256

Chromatographic Conditions 256

Hydrolysis Conditions 256

Postcolumn Derivatization Conditions 257

Fluorometer Conditions 257

Extraction 257

Urea Pesticides 257

Column 258

Liquid Chromatograph 258

Mass Spectrometer 259

Precision and Accuracy 259

Triazine Pesticides 259


Chapter 46 Pesticides: Organochlorine 261


Analysis 263

Air Analysis 266

References 266

Chapter 47 Pesticides: Organophosphorus 267

Analysis of Aqueous and Solid Samples 267


Air Analysis 272

Reference 272

Chapter 48 pHandEh 273

Eh 274

Chapter 49 Phenols 277

Extraction 277

Analysis 278

Derivatization 278

Air Analysis 280

Chapter 50 Phosphorus 281

Analysis 281

Sample Presentation 281

Colorimetric Analysis 282

Interference 282

Calibration Standards 283

Ion Chromatography 283

Chapter 51 Phthalate Esters 285

Air Analysis 287

xvi Contents

Chapter 52 Polychlorinated Biphenyls 289

Quantitation 290


Alternate Analytical Methods 291

Air Analysis 291

Chapter 53 Polychlorinated Dioxins and Dibenzofurans 293

Analysis 293


Acid-Base Partitioning 294

Alumina Cleanup 294

Silica Gel Cleanup 294

Carbon Column Cleanup 294

GC/MS Analysis 294

Sample Preservation and Holding Time 295

References 295

Chapter 54 Radioactivity 297

Units of Measurement 297

Instruments for Measuring Radioactivity 298

Gas-Flow Proportional Counters 298

Alpha Scintillation Counters 299

Liquid Scintillation Counters 299

Alpha Spectrometers 299

Gamma Spectrometers 300

Determination of Gross Alpha and Gross Beta Radioactivity 300

Evaporation Method 300

Gross Activity of the Sample 300

Activity of Dissolved and Suspended Matter 301

Activity of Semisolid Samples 301

Coprecipitation Method for Gross Alpha Activity 302

Procedure 303

Specific Radionuclides 303

Radium 304

Precipitation Method and Alpha Counting 304

Precipitation and Emanation Method to Measure Radium as Radon-222 305

Sequential Precipitation Method 305

Measurement of Radium-224 by Gamma Spectroscopy 306

Radon 306

Uranium 307

Determination of Total Alpha Activity 307

Determination of Isotopic Content of Uranium Alpha Activity 307

Radioactive Strontium 308

Tritium 310

Radioactive Iodine 310

Precipitation Method 311

Ion-Exchange Method 311

Distillation Method 312

Radioactive Cesium 313

Contents xvii

Preparation of Ammonium Phosphomolybdate, (NH^PMo^O^ ReagentSolution 314

References 314

Chapter 55 Semivolatile Organic Compounds 315

Sampling and Storage 327

References 327

Chapter 56 Silica 329

Gravimetric Method 329Procedure 329

Ammonium Molybdate Colorimetric Method 330

Procedure 330

Reagent 331

Chapter 57 Sulfate 333

Gravimetric Method 333Interference 333Procedure 333Calculation 334

Turbidimetric Method 334Procedure 334

Calculation 334

Reagents 334

Chapter 58 Sulfide 337

Analysis of Sulfide in Water 337

Screening Test for Sulfide 337

Sample Pretreatment 337

Analysis of Dissolved Sulfide in Water 338Iodometric Method 339

Procedure 339Calculation 339

Reagents 340

Methylene Blue Colorimetric Method 340Procedure 341

Methylene Blue Solution: Preparation and Standardization 341

Standardization 342

Reagents 342

Chapter 59 Sulfite 343

Iodometric Method 343

Interference 343

Procedure 344

Calculation 344

Reagents 344

xviiiContents

Colorimetric Method344

Procedure345

Calculation345

Reagents346

Chapter 60 Surfactant: Anionic 347

Reagents347

Analysis347

Sample Analysis349

Calculation349

Interference349

Chapter 61 Thiocyanate351

Colorimetric Method351

Interference351

Procedure351

Calculation351

Reagents and Calibration Standards 352

Spot Test for Thiocyanate352

Procedure352

Reagents353

Chapter 62 Total Dissolved Solids and Specific Conductance: Theoretical Calculations 355

Total Dissolved Solids355

Conductivity355

Chapter 63 Volatile Organic Compounds361

Water Analysis361

Apparatus362

GC and MS Conditions 362

Soil, Sediments, and Solid Waste363

U.S. EPA's SW Methods 363

Air Analysis366

U.S. EPA Method TO-14A 367

U.S. EPA's Solid Wastes 846 Methods 369

NIOSH Method 2549 369

GC Column and Conditions 370

MS Conditions370

References372

SECTION III Selected Individual Compounds

Chapter 64 Acetaldehyde375

Analysis of Aqueous Sample375

Air Analysis375

References376

Contents x'x

Chapter 65 Acetone 377

Analysis of Aqueous Samples 377

Air Analysis 377

Reference 378

Chapter 66 Acetonitrile 379

Analysis of Aqueous and Nonaqueous Samples 379

Air Analysis 379

Reference 379

Chapter 67 Acrolein 381


Air Analysis 381

Reference 381

Chapter 68 Acrylonitrile 383


Air Analysis 383

References 384

Chapter 69 Aniline 385

Description 385


Air Analysis 385

Reference 385

Chapter 70 Arsine 387

Air Analysis 387

Chapter 71 Asbestos 389

Analysis 389

Analysis of Aqueous Samples 389Air Analysis 390

Reference 390

Chapter 72 Benzene 391

Analysis of Aqueous and Nonaqueous Samples 391Air Analysis 391

Chapter 73 Benzidine 393


Chapter 74 Benzyl Chloride 395

Description 395


Air Analysis 395

xx Contents

Chapter 75 1,3-Butadiene 397

Air Analysis 397

Reference 397

Chapter 76 Carbon Disulfide 399

Description 399


Air Analysis 399

References 399

Chapter 77 Carbon Monoxide 401

Air Analysis 401

Reference 401

Chapter 78 Carbon Tetrachloride 403


Air Analysis 403

Chapter 79 Captan 405


Reference 405

Chapter 80 Chloroacetic Acid 407


Air Analysis 408

References 408

Chapter 81 Chlorobenzene 409


Air Analysis 409

Chapter 82 Chloroform 411


Air Analysis 411

Chapter 83 2-Chlorophenol 413


Air Analysis 413

Chapter 84 Cumene 415


Air Analysis 415

Reference 416

Contents xxi

Chapter 85 Cyanogen 417

Air Analysis (Suggested Method) 417

OSHA Method PV2104 417

Reference 417

Chapter 86 Cyanuric Acid 419


Air Analysis 419

Chapter 87 Diazomethane 421

Air Analysis 421

Chapter 88 Diborane 423

Air Analysis 423

Chapter 89 Dichlorobenzene 425


Air Analysis 425

Chapter 90 1,1-Dichlorethylene 427


Air Analysis 427

Chapter 91 2,4-Dichlorophenol 429


Air Analysis 429

Reference 429

Chapter 92 Diethyl Ether 431


Air Analysis 431

References 431

Chapter 93 2,4-Dinitrotoluene 433


Chapter 94 2,6-Dinitrotoluene 435


Chapter 95 Epichlorohydri n 437


Air Analysis 437

Reference 437

xxii Contents

Chapter 96 Ethylbenzene 439


Air Analysis 439

References 440

Chapter 97 Ethyl Chloride 441


Air Analysis 441

Chapter 98 Ethylene Chlorohydrin 443

Analysis of Aqueous Sample 443

Air Analysis 443

Reference 443

Chapter 99 Ethylene Dibromide 445


Air Analysis 445

Reference 445

Chapter 100 Ethylene Glycol 447

Analysis of Aqueous and Nonaqueous Samples (Suggested Method) 447

Air Analysis 447

References 447

Chapter 101 Ethylene Oxide 449

Air Analysis 449

References 449

Chapter 102 Formaldehyde 451

Water Analysis 451

Air Analysis 451

References 452

Chapter 103 Freon 113 453


Air Analysis 453

Reference 453

Chapter 104 Hydrogen Cyanide 455


Air Analysis 455

References 456

Contents xx»'

Chapter 105 Hydroquinone 457


Air Analysis 457

Reference 457

Chapter 106 Hydrogen Sulfide 459

Air Analysis 459

References 459

Chapter 107 Isophorone 461


Chapter 108 Methane 463

Analysis of Aqueous Samples and Sludge Digester Gas 463

Air Analysis 463

Chapter 109 Methyl Bromide 465


Air Analysis 465

Chapter 110 Methyl Chloride 467


Air Analysis 467

Chapter 111 Methylene Chloride 469


Air Analysis 469

Chapter 112 Methyl Iodide 471


Air Analysis 471

Chapter 113 Methyl Isobutyl Ketone 473

Analysis of Aqueous and Nonaqueous Samples 473Air Analysis 473References 474

Chapter 114 Methyl Isocyanate 475

Air Analysis 475

Reference 475

Chapter 115 Methyl Methacrylate 477


xxiv Contents

Air Analysis 477

Reference 477

Chapter 116 Nitrobenzene 479


Air Analysis 479

Reference 479

Chapter 117 Nitrogen Dioxide 481

Air Analysis 481

Reference 481

Chapter 118 Pentachlorophenol 483


Air Analysis 483

References 484

Chapter 119 Phosgene 485

Air Analysis 485

Reference 485

Chapter 120 Pyridine 487


Air Analysis 487

Reference 487

Chapter 121 Pyrocatechol 489


Air Analysis 489

Chapter 122 Pyrogallol 491


Air Analysis 491

Chapter 123 Resorcinol 493


Air Analysis 493

Chapter 124 Stibine 495

Air Analysis 495

Reference 495

Chapter 125 Strychnine 497


Contents xxv

Air Analysis 497

Reference 497

Chapter 126 Styrene 499


Air Analysis 499

Reference 500

Chapter 127 Sulfur Dioxide 501

Air Analysis 501

References 501

Chapter 128 Tetrachloroethylene 503


Air Analysis 503

Reference 503

Chapter 129 Tetraethyllead 505


References 505

Chapter 130 Tetraethyl Pyrophosphate 507


Air Analysis 507

Reference 507

Chapter 131 Tetrahydrofuran 509


Air Analysis 509

Reference 509

Chapter 132 Toluene 511


References 512

Chapter 133 Toluene-2,4-Diisocyanate 513


Air Analysis 514

References, 514

Chapter 134 o-Toluidine 515


Air Analysis 515

Reference 515

xxvi Contents

Chapter 135 1,1,1-Trichloroethane 517


Air Analysis 517

Reference 517

Chapter 136 Trichloroethylene 519


Air Analysis 519

References 520

Chapter 137 2,4,6-Trichlorophenol 521


Air Analysis 521

Chapter 138 Vinyl Chloride 523


Air Analysis 523

References 523

Chapter 139 Xylene 525


Air Analysis 526

Appendix A: Some Common QC Formulas and Statistics 527

Appendix B: Sample Containers, Preservations, and Holding Times 531

Appendix C: Preparation of Molar and Normal Solutions of Some Common Reagents 535

Appendix D: Characteristic Masses of Miscellaneous Organic Pollutants

(Not Listed in Text) for GC/MS Identification 537

Appendix E: Volatility of Some Additional Organic Substances (Not Listed in Text)

for Purge and Trap Analysis 541

Appendix F: NIOSH Methods for Air Analysis 545

Appendix G: U.S. EPA Methods for Air Analysis 553

Appendix H: Inorganic Test Procedures for Analysis of Aqueous Samples: EPA,

SM, and ASTM Reference Methods 557

Appendix I: U.S. EPA's Analytical Methods for Organic Pollutants in Aqueousand Solid Matrices 565

Chemical Compounds Index 587

CAS Registry Numbers Index 605

Subject Index 617

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