Handbook Of Environmental Analysis : Chemical Pollutants In Air, Water .

Handbook of Environmental Analysis Chemical Pollutants in Air, Water, Soil, and Solid Wastes Third Edition Pradyot CRC Press is an imprint Taylor & Francis Group, Patnaik of the an Informa business

Contents Preface xxvii Acknowledgments xxix Author xxxi SECTION I Chapter 1 Chapter 2 Analytical Techniques Environmental Precision and Analysis: An Overview of Accuracy 3 5 Analysis Statistics in Environmental Quality Analysis Quality Control Assurance and Precision and 5 in Environmental Analysis 6 Accuracy Control Charts Chapter 3 Analysis of 13 Organic Pollutants by Gas Chromatography 16 Detectors 18 Calibration 18 19 External Standard Calibration 19 Alternative Calculation 20 Internal Standard Method 21 Routine 4 15 Selection of Column Calculations Chapter 6 21 Analysis Analysis of Organic Pollutants by Gas Chromatography/Mass Spectrometry Terms and Definitions of Mass Application Interpretation 23 23 Spectrometry Spectra of Mass Number of Carbon Atoms 23 24 26 Nitrogen Rule 26 Index of Hydrogen Deficiency 26 Determination of Molecular Formula 26 Chemical Ionization 27 Limitation of GC/MS Analysis U.S. EPA Methods Volatile Organics by Purge and Trap Method Semivolatile Organics Tuning Compound Identification Calibration References 28 28 29 30 30 32 32 34

viii Contents Chapter 5 Extraction of Organic Pollutants and Sample Cleanup Sample Extraction 35 Liquid-Liquid Extraction 35 Solid Phase Extraction 36 Soxhlet Extraction 37 Supercritical Fluid Cleanup Extraction 37 37 Acid-Base Partitioning Alumina Column Cleanup 38 Silica Gel Cleanup 38 Florisil Column 39 Gel-Permeation 38 Cleanup Cleanup 39 Sulfur 39 Cleanup Permanganate-Sulfuric Chapter 6 Titrimetric Acid Cleanup Analysis 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 54 Na2S203 Starch Indicator 55 Titration Argentometric Complexometric 55 Titrations 57 Potentiometric Titration 59 End Point Detection 59 Chapter 7 Colorimetric Chapter 8 Analysis 63 Analysis of Metals by Atomic Absorption and Emission Spectroscopy 67 Sample Digestion for Metals Atomic Absorption Spectrometry 68 Chelation-Extraction Method 70 Hydride Generation Method Cold Vapor Method for Mercury Accuracy in Quantitation 68 71 Determination Standard Addition ICP Mass Spectroscopy Environmental 72 72 74 Spectrometry Ion-Selective Electrodes 71 72 Atomic Emission Plasma 9 39 41 Acid-Base Titration Chapter 35 Analysis Sample Analysis Standard Calibration Method 77 77 78

Contents Chapter ix 10 Standard Addition Method 79 Sample Addition Method 80 Application of Environmental Chapter Chapter 11 12 Ion High-Performance Liquid Chromatography Analysis in 81 Chromatography 85 References 88 Air 89 Analysis Sampling Plan Air Sampling 89 90 Direct Collection of Air 90 Use of Adsorbent Tubes Air Sampling 90 for Particulates and Inorganic Substances 91 Flow Rate 91 Chemical Analysis Calculation Chapter Chapter 13 14 Application of 92 92 Immunoassay Techniques in Environmental 98 Calculation 98 Derivatization Reactions in Trace Chemical Analysis 101 Derivatization Reactions: General Discussion 101 Alkylation 102 Acylation 104 Sylilation 105 106 Selection of Derivatizing 15 97 Extraction Diazotization Chapter Analysis Reagent 106 Microbial Analysis 109 Coliform 109 Groups of Bacteria Sample Collection, Preservation, and Storage MF Method for Testing TCs and E. coli Outline of the Method Quality 110 110 Interference Reagents, Standards, 110 Ill and Equipment Control Ill 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

Contents x SECTION II Specific Classes of Substances and Aggregate Properties Chapter 16 Aldehydes and Ketones 119 Derivatization with 2,4-PNPH 119 Columns and Conditions Chapter 17 Chapter 18 Chromatographic Sample Collection and Holding Time Air Analysis 122 Alkalinity 125 Calculation 125 Bromide 127 Phenol Red Colorimetric Method 127 127 Reagents 127 128 Determination of Bromide Plus Iodide 128 Procedure 128 Determination of Iodide 129 Calculation 19 129 Chloride 131 Mercuric Nitrate Titrimetric Method 131 Procedure 131 Reagents 132 Argentometric Titrimetric Method 132 Procedure 132 133 Reagents Automated Ferricyanide Colorimetric Method Procedure 133 133 133 Reagents Gravimetric Determination of Chloride Chapter 20 122 Procedure Titrimetric Method Chapter 122 134 Procedure 134 Calculation 134 Chlorine and Chloramines 135 General Discussion Colorimetric Methods for Chlorine 135 Analysis DPD Colorimetric Test Syringaldazine Colorimetric Test 137 Orthotolidine Colorimetric Test Titrimetric Procedures for Chlorine DPD Titration Method Iodometric Back Titration Method Chloramines 136 136 137 Analysis 137 137 139 139

Contents Chapter Chapter xi 21 22 Cyanate 141 Calculation 141 Procedure 141 Cyanide, Total 143 Silver Nitrate Titrimetric Method 143 Procedure 143 Reagents 144 Colorimetric Method 144 Procedure Preparation Reagents of 145 Cyanide Chapter Chapter Chapter 23 24 25 145 146 Determination of Cyanides Standards and Calibration Curve Cyanide in Soil, Sediment, and Solid Waste in Aerosol and Gas Cyanide Amenable 147 to Chlorination 149 Procedure 149 Alternative Procedure 149 Reagents 150 Emerging Pollutants: Classification, Extractions, and Analytical Techniques—An Overview 151 General Definition and Classifications 151 Sample Extractions Analysis 154 151 Emerging Pollutants: Ethoxylates Nonionic Surfactants—Alkylphenols and Their 155 Structures 155 Sample Extractions and Analysis: General Discussion SPE-LC/MS Method (LC Tandem MS [LC-MS/MS]) SPE-GC/MS Method References Chapter 26 27 156 158 159 160 Emerging Pollutants: Organophosphate Flame Retardants, Plasticizers, and Lubricants 163 Analysis of 166 Indoor Dust References Chapter 146 166 Emerging Pollutants: Pharmaceuticals and Personal Care Products U.S. EPA Method 1694. of the Method 167 167 Summary Sample Preparation Sample Cleanup 167 LC-MS/MS Analysis Qualitative Determination and Quantification 173 169 173 175

xii Contents Quality Assurance/Quality Control Sample Collection, Preservation, and Holding 176 Time 176 References Chapter 28 Emerging 177 Pollutants: Steroids and Hormones 179 Outline of the Procedure Sample Collection, Chapter 29 179 Preservation, and 181 Storage GC Conditions 181 MS Conditions 181 Calibration and Quantitation 181 Quality Control 184 References 184 Emerging 185 Pollutants: Nanomaterials 185 Classifications and Uses Separation, Characterization, and Food and Agricultural Samples Environmental Samples Chapter 30 Detection of Nanoparticles Fluorides Procedure 31 Chapter 32 Chapter 33 187 189 189 Automated Colorimetric Method 189 Haloacetic Acids 191 Alternative Methods 191 References 192 Halogenated Hydrocarbons 193 Solvent Extraction 194 Sample Collection and Preservation Internal Standards/Surrogates and Tuning Compounds 197 Air Analysis 197 197 201 Hardness 201 Hardness Determinations Chapter 34 185 189 Colorimetric SPADNS Method Chapter in Calculation 201 Titration 201 Herbicides: Chlorophenoxy Acid Analysis Sample Extraction Hydrolysis 203 203 203 204 Esterification 204 Gas 206 Air Chromatographic Analysis Analysis 206

Contents Chapter 35 xiii Herbicides: Glyphosate Water 209 Analysis 209 HPLC Method Sampling and 209 Storage 209 Detection Limit 210 Miscellaneous Methods for Analysis of GLYPH Residues in Water, Soil, Sludge, Fruit, Chapter 36 and Vegetable Extracts 211 Hydrocarbons 213 Analysis 213 Total Petroleum Hydrocarbons Gasoline Range Organics Diesel Range Organics Chapter 37 214 214 217 HPLC Columns and Conditions 217 GC Columns and Conditions 218 Sample Extraction Air Analysis 218 and Cleanup 219 220 Reference 220 Nitrogen (Ammonia) 221 Sample Distillation Reagents 222 Titrimetric Method 222 221 Reagents 222 Colorimetric Nesslerization Method 223 Procedure 223 Calculation 223 and Standards Reagents Colorimetric Phenate Method 224 224 Procedure 225 Calculation 225 Reagents and Standards Ion-Selective Electrode Reagents 225 226 Procedure Chapter 39 213 Hydrocarbons, Polynuclear Aromatic MS Conditions Chapter 38 210 References 226 and Standards 227 AIR ANALYSIS 227 References 228 Nitrogen (Nitrate) 229 Cadmium Reduction Method Procedure Apparatus, Reagents, 229 230 and Standards Miscellaneous Reduction Method 230 231

xiv Contents Nitrate Electrode Method Chapter 40 Chapter 41 231 Procedure 231 Reagents 231 Nitrosamines 233 Extraction 234 Analysis Air Analysis 235 References 236 Oil and Grease 237 Partition-Gravimetry Method 237 235 Calculation 238 Partition-Infrared Method 238 Solid Phase Partition-Gravimetric Method 239 Hydrocarbons 239 Sample Collection and Preservation References Chapter 42 240 Oxygen Demand, Graphical Biochemical Calculation 242 Measurement of DO Iodometric or 243 Winkler Method Electrode Method Kinetics of BOD Reaction 244 Reference 245 Oxygen Demand, Chemical 247 Standardization of FAS Titrant 249 249 Sample Treatment 249 Colorimetric Analysis 250 Oxyhalides 251 Analysis Chapter 45 243 244 Indicator Solution Chapter 44 241 242 Method Chapter 43 240 of Oxyhalides by U.S. EPA Methods 251 U.S. EPA Method 300.1 251 U.S. EPA Method 317.0 252 Interference 252 Sample Collection, Preservation, and Storage Quality Control 253 253 Miscellaneous Methods 253 References 254 Pesticides: Carbamate, Urea, and Triazine 255 Carbamate Pesticides 255

Contents xv LC Columns Chromatographic Hydrolysis 256 Conditions 256 Conditions 256 Postcolumn Derivatization Conditions 257 Fluorometer Conditions 257 Extraction 257 Urea Pesticides 257 Column 258 Liquid Chromatograph Mass Spectrometer Precision and Accuracy 258 259 259 Triazine Pesticides Sample Chapter Chapter 46 47 Pesticides: Chapter 49 260 Organochlorine 263 References 266 Pesticides: 261 266 Organophosphorus and Solid 51 267 271 272 pHandEh 273 Eh 274 Phenols 277 Extraction 277 Analysis 278 Analysis 278 280 Phosphorus 281 Analysis Sample Presentation Colorimetric Analysis 281 281 282 Interference 282 Calibration Standards 283 Ion Chapter Samples 272 Air 50 267 Reference Derivatization Chapter 261 Sample Extraction Analysis Air Analysis Analysis of Aqueous Sample Extraction Air Analysis Chapter 48 259 Extraction Chromatography 283 Phthalate Esters 285 Air 287 Analysis

xvi Contents Chapter 52 Polychlorinated Biphenyls 289 Quantitation 290 Sample Extraction and Alternate Air Chapter 53 Analytical 291 Cleanup Methods 291 291 Analysis Polychlorinated Dioxins and Dibenzofurans 293 Analysis Sample Extraction and Cleanup Acid-Base Partitioning Alumina Cleanup Silica Gel Cleanup Carbon Column Cleanup GC/MS Analysis Sample Preservation and Holding Chapter 54 293 293 294 294 294 294 294 Time 295 References 295 Radioactivity 297 297 Units of Measurement Instruments for Gas-Flow 298 Measuring Radioactivity Proportional 298 Counters Alpha Liquid Scintillation Counters Alpha Spectrometers Gamma Spectrometers Determination of Gross Alpha and Gross Beta Radioactivity Evaporation Method Gross Activity of the Sample Activity of Dissolved and Suspended Matter Activity of Semisolid Samples Coprecipitation Method for Gross Alpha Activity 299 Procedure 303 Scintillation Counters Specific 299 299 300 300 300 300 301 301 302 Radionuclides 303 Radium 304 Precipitation Method and Precipitation and Emanation Method to Measure Radium Sequential Precipitation 304 Alpha Counting as Radon-222 Method Measurement of Radium-224 by 305 305 Gamma Spectroscopy 306 Radon 306 Uranium 307 Determination of Total Determination of Alpha Activity Isotopic Content of Uranium Alpha Activity 307 307 Radioactive Strontium 308 Tritium 310 Radioactive Iodine Method 310 Precipitation Ion-Exchange Method 311 Distillation Method 312 Radioactive Cesium 313 311