Preface ...................................................... xvii
1. Introduction to Environmental Data Acquisition .............. 1
1.1. Introduction .......................................... 1
1.1.1. Importance of Scientifically Reliable and
Legally Defensible Data ....................... 2
1.1.2. Sampling Error vs. Analytical Error During
Data Acquisition .............................. 4
1.2. Environmental Sampling ................................ 5
1.2.1. Scope of Environmental Sampling ............... 5
1.2.2. Where, When, What, How, and How Many .......... 6
1.3. Environmental Analysis ................................ 6
1.3.1. Uniqueness of Modern Environmental Analysis ... 7
1.3.2. Classical and Modern Analytical and
Monitoring Techniques ......................... 7
References .................................................. 9
Questions and Problems ..................................... 10
2. Basics of Environmental Sampling and Analysis .............. 11
2.1. Essential Analytical and Organic Chemistry ........... 11
2.1.1. Concentration Units .......................... 11
2.1.2. Common Organic Pollutants and Their
Properties ................................... 14
2.1.3. Analytical Precision, Accuracy, and
Recovery ..................................... 16
2.1.4. Detection Limit and Quantitation Limit ....... 17
2.1.5. Standard Calibration Curve ................... 18
2.2. Essential Environmental Statistics ................... 20
2.2.1. Measurements of Central Tendency and
Dispersion ................................... 20
2.2.2. Understanding Probability Distributions ...... 21
2.2.3. Type I and II Errors: False Positive and
False Negative ............................... 25
2.2.4. Detection of Outliers ........................ 26
2.2.5. Analysis of Censored Data .................... 28
2.2.6. Analysis of Spatial and Time Series Data ..... 29
2.3. Essential Hydrology and Geology ...................... 30
2.3.1. Stream Water Flow and Measurement ............ 30
2.3.2. Groundwater Flow in Aquifers ................. 31
2.3.3. Groundwater Wells ............................ 32
2.4. Essential Knowledge of Environmental Regulations ..... 35
2.4.1. Major Regulations Administrated by
the U.S. EPA ................................. 35
2.4.2. Other Important Environmental Regulations .... 35
References ................................................. 37
Questions and Problems ..................................... 39
3. Environmental Sampling Design .............................. 45
3.1. Planning and Sampling Protocols ...................... 45
3.1.1. Data Quality Objectives ...................... 46
3.1.2. Basic Considerations of Sampling Plan ........ 48
3.2. Sampling Environmental Population .................... 49
3.2.1. Where (Space) and When (Time) to Sample ...... 49
3.2.2. Obtain Representative Samples from Various
Matrices ..................................... 49
3.3. Environmental Sampling Approaches: Where and When .... 52
3.3.1. Judgmental Sampling .......................... 52
3.3.2. Simple Random Sampling ....................... 53
3.3.3. Stratified Random Sampling ................... 54
3.3.4. Systematic Sampling .......................... 56
3.3.5. Other Sampling Designs ....................... 57
3.4. Estimating Sample Numbers: How Many Samples
are Required ......................................... 61
References ................................................. 63
Questions and Problems ..................................... 63
4. Environmental Sampling Techniques .......................... 69
4.1. General Guidelines of Environmental Sampling
Techniques ........................................... 69
4.1.1. Sequence of Sampling Matrices and Analytes ... 70
4.1.2. Sample Amount ................................ 70
4.1.3. Sample Preservation and Storage .............. 71
4.1.4. Selection of Sample Containers ............... 74
4.1.5. Selection of Sampling Equipment .............. 76
4.2. Techniques for Sampling Various Media: Practical
Approaches and Tips .................................. 83
4.2.1. Surface Water and Wastewater Sampling ........ 84
4.2.2. Groundwater Sampling ......................... 86
4.2.3. Soil and Sediment Sampling ................... 89
4.2.4. Hazardous Waste Sampling ..................... 90
4.2.5. Biological Sampling .......................... 92
4.2.6. Air and Stack Emission Sampling .............. 92
References ................................................. 93
Questions and Problems ..................................... 94
5. Methodology and Quality Assurance/Quality Control of
Environmental Analysis ..................................... 97
5.1. Overview on Standard Methodologies ................... 98
5.1.1. The U.S. EPA Methods for Air, Water,
Wastewater, and Hazardous Waste .............. 98
5.1.2. Other Applicable Methods:
APHA/ASTM/OSHA/NIOSH/USGS/AOAC .............. 103
5.2. Selection of Standard Methods ....................... 108
5.2.1. Methods for Sample Preparation .............. 109
5.2.2. Methods for Physical, Biological, and
General Chemical Parameters ................. 111
5.2.3. Methods for Volatile Organic Compounds
(VOCs) ...................................... 112
5.2.4. Methods for Semivolatile Organic Compounds
(SVOCs) ..................................... 113
5.2.5. Methods for Other Pollutants and Compounds
of Emerging Environmental Concerns .......... 113
5.3. Field Quality Assurance/Quality Control (QA/QC) ..... 115
5.3.1. Types of Field QA/QC Samples ................ 116
5.3.2. Numbers of Field QA/QC Samples .............. 118
5.4. Analytical Quality Assurance/Quality Control ........ 118
5.4.1. Quality Control Procedures for Sample
Preparation ................................. 118
5.4.2. Quality Control Procedures During
Analysis .................................... 119
References ................................................ 122
Questions and Problems .................................... 123
6. Common Operations and Wet Chemical Methods in
Environmental Laboratories ................................ 127
6.1. Basic Operations in Environmental Laboratories ...... 128
6.1.1. Labware Cleaning Protocols for Trace
Analysis .................................... 128
6.1.2. Chemical Reagent Purity, Standard, and
Reference Materials ......................... 129
6.1.3. Volumetric Glassware and Calibration ........ 132
6.1.4. Laboratory Health, Safety, and Emergency
First Aid ................................... 134
6.1.5. Waste Handling and Disposal ................. 136
6.2. Wet Chemical Methods and Common Techniques in
Environmental Analysis .............................. 137
6.2.1. Gravimetric and Volumetric Wet Chemical
Methods ..................................... 137
6.2.2. Common Laboratory Techniques ................ 138
6.3. Analytical Principles for Common Wet Chemical
Methods ............................................. 141
6.3.1. Moisture in Solid and Biological Samples .... 141
6.3.2. Solids in Water, Wastewater, and Sludge
(TS, TSS, TDS, VS) .......................... 141
6.3.3. Acidity, Alkalinity, and Hardness
of Waters ................................... 142
6.3.4. Oxygen Demand in Water and Wastewater
(DO, BOD and COD) ........................... 145
6.3.5. Oil and Grease in Water and Wastewater ...... 148
6.3.6. Residual Chlorine and Chloride in
Drinking Water .............................. 149
6.3.7. Ammonia in Wastewater ....................... 152
6.3.8. Cyanide in Water, Wastewater and
Soil Extract ................................ 153
6.3.9. Sulfide in Water and Waste .................. 154
References ................................................ 155
Questions and Problems .................................... 155
7. Fundamentals of Sample Preparation for
Environmental Analysis .................................... 159
7.1. Overview on Sample Preparation ...................... 160
7.1.1. Purpose of Sample Preparation ............... 160
7.1.2. Types of Sample Preparation ................. 161
7.2. Sample Preparation for Metal Analysis ............... 162
7.2.1. Various Forms of Metals and Preparation
Methods ..................................... 162
7.2.2. Principles of Acid Digestion and Selection
of Acid ..................................... 163
7.2.3. Alkaline Digestion and Other Extraction
Methods ..................................... 165
7.3. Extraction for SVOC and Non-VOC from Liquid or
Solid Samples ....................................... 168
7.3.1. Separatory Funnel and Continuous
Liquid-Liquid Extraction (LLE) .............. 168
7.3.2. Solid Phase Extraction ...................... 171
7.3.3. Solid Phase Microextraction ................. 173
7.3.4. Soxhlet and Automatic Soxhlet Extraction
(Soxtec) .................................... 174
7.3.5. Ultrasonic Extraction ....................... 176
7.3.6. Pressured Fluid Extraction .................. 177
7.3.7. Supercritical Fluid Extraction .............. 177
7.3.8. Comparison and Selection of Organic
Extraction Methods .......................... 178
7.4. Post-Extraction Clean-up of Organic Compounds ....... 179
7.4.1. Theories and Operation Principles of
Various Clean-up Methods .................... 179
7.4.2. Recommended Clean-up Method for Selected
Compounds ................................... 181
7.5. Derivatization of Non-VOC for Gas Phase Analysis .... 182
7.6. Sample Preparation for VOC, Air and Stack Gas
Emission ........................................... 183
7.6.1. Dynamic Headspace Extraction
(Purge-and-Trap) ............................ 183
7.6.2. Static Headspace Extraction ................. 184
7.6.3. Azeotropic and Vacuum Distillation .......... 185
7.6.4. Volatile Organic Sampling Train ............. 186
References ................................................ 187
Questions and Problems .................................... 187
8. UV-Visible and Infrared Spectroscopic Methods in
Environmental Analysis .................................... 190
8.1. Introduction to the Principles of Spectroscopy ...... 191
8.1.1. Understanding the Interactions of Various
Radiations with Matter ...................... 191
8.1.2. Origins of Absorption in Relation to
Molecular Orbital Theories .................. 193
8.1.3. Molecular Structure and UV-
Visible/Infrared Spectra .................... 200
8.1.4. Quantitative Analysis with Beer-Lambert's
Law ......................................... 204
8.2. UV-Visible Spectroscopy ............................. 206
8.2.1. UV-Visible Instrumentation .................. 206
8.2.2. UV-VIS as a Workhorse in Environmental
Analysis .................................... 208
8.3. Infrared Spectroscopy ............................... 211
8.3.1. Fourier Transform Infrared Spectrometers
(FTIR) ...................................... 211
8.3.2. Dispersive Infrared Instruments (DIR) ....... 213
8.3.3. Nondispersive Infrared Instruments (NDIR) ... 214
8.3.4. Applications in Industrial Hygiene and Air
Pollution Monitoring ........................ 214
8.4. Practical Aspects of UV-Visible and Infrared
Spectrometry ........................................ 215
8.4.1. Common Tips for UV-Visible Spectroscopic
Analysis .................................... 215
8.4.2. Sample Preparation for Infrared
Spectroscopic Analysis ...................... 216
References ................................................ 217
Questions and Problems .................................... 218
9. Atomic Spectroscopy for Metal Analysis .................... 220
9.1. Introduction to the Principles of Atomic
Spectroscopy ........................................ 221
9.1.1. Flame and Flameless Atomic Absorption ....... 221
9.1.2. Inductively Coupled Plasma Atomic
Emission .................................... 225
9.1.3. Atomic X-ray Fluorescence ................... 227
9.2. Instruments for Atomic Spectroscopy ................. 227
9.2.1. Flame and Flameless Atomic Absorption ....... 227
9.2.2. Cold Vapor and Hydride Generation Atomic
Absorption .................................. 229
9.2.3. Inductively Coupled Plasma Atomic
Emission .................................... 232
9.2.4. Atomic X-ray Fluorescence ................... 233
9.3. Selection of the Proper Atomic Spectroscopic
Techniques .......................................... 235
9.3.1. Comparison of Detection Limits and
Working Range ............................... 235
9.3.2. Comparison of Interferences and Other
Considerations .............................. 236
9.4. Practical Tips to Sampling, Sample Preparation,
and Metal Analysis .................................. 240
References ................................................ 243
Questions and Problems .................................... 243
10. Chromatographic Methods for Environmental Analysis ........ 246
10.1. Introduction to Chromatography ...................... 247
10.1.1. Types of Chromatography and Separation
Columns ..................................... 247
10.1.2. Common Stationary Phases: The Key to
Separation .................................. 249
10.1.3. Other Parameters Important to Compound
Separation .................................. 251
10.1.4. Terms and Theories of Chromatogram .......... 254
10.1.5. Use of Chromatograms for Qualitative and
Quantitative Analysis ....................... 258
10.2. Instruments of Chromatographic Methods .............. 258
10.2.1. Gas Chromatography .......................... 258
10.2.2. High Performance Liquid Chromatography
(HPLC) ...................................... 260
10.2.3. Ion Chromatography .......................... 264
10.2.4. Supercritical Fluid Chromatography .......... 265
10.3. Common Detectors for Chromatography ................. 266
10.3.1. Detectors for Gas Chromatography ............ 267
10.3.2. Detectors for High Performance Liquid
Chromatography .............................. 272
10.3.3. Detectors for Ion Chromatography ............ 274
10.4. Applications of Chromatographic Methods
in Environmental Analysis ........................... 275
10.4.1. Gases, Volatile, and Semivolatile Organics
with GC ..................................... 276
10.4.2. Semivolatile and Nonvolatile Organics with
HPLC ........................................ 278
10.4.3. Ionic Species with IC ....................... 278
10.5. Practical Tips to Chromatographic Methods ........... 279
10.5.1. What Can and Cannot be Done with GC
and HPLC .................................... 279
10.5.2. Development for GC and HPLC Methods ......... 280
10.5.3. Overview on Maintenance and
Troubleshooting ............................. 281
References ................................................ 284
Questions and Problems .................................... 285
11. Electrochemical Methods for Environmental Analysis ........ 289
11.1. Introduction to Electrochemical Theories ............ 290
11.1.1. Review of Redox Chemistry and
Electrochemical Cells ....................... 290
11.1.2. General Principles of Electroanalytical
Methods ..................................... 292
11.1.3. Types of Electrodes and Notations for
Electrochemical Cells ....................... 295
11.2. Potentiometric Applications in Environmental
Analysis ............................................ 296
11.2.1. Measurement of pH ........................... 296
11.2.2. Measurement of Ions by Ion Selective
Electrodes (ISEs) ........................... 298
11.2.3. Potentiometric Titration (Indirect
Potentiometry) .............................. 299
11.3. Voltammetric Applications in Environmental
Analysis ............................................ 300
11.3.1. Measurement of Dissolved Oxygen ............. 300
11.3.2. Measurement of Anions by Amperometric
Titration ................................... 302
11.3.3. Measurement of Metals by Anodic Stripping
Voltammetry (ASV) ........................... 303
References ................................................ 305
Questions and Problems .................................... 306
12. Other Instrumental Methods in Environmental Analysis ...... 309
12.1. Hyphenated Mass Spectrometric Methods and
Applications ........................................ 310
12.1.1. Atomic Mass Spectrometry (ICP-MS) ........... 310
12.1.2. Molecular Mass Spectrometry (GC-MS
and LC-MS) .................................. 313
12.1.3. Mass Spectrometric Applications in
Environmental Analysis ...................... 320
12.2. Nuclear Magnetic Resonance Spectroscopy (NMR) ....... 322
12.2.1. NMR Spectrometers and the Origin of NMR
Signals ..................................... 322
12.2.2. Molecular Structures and NMR Spectra ........ 325
12.2.3. Applications of NMR in Environmental
Analysis .................................... 329
12.3. Miscellaneous Methods ............................... 329
12.3.1. Radiochemical Analysis ...................... 329
12.3.2. Surface and Interface Analysis .............. 333
12.3.3. Screening Methods Using Immunoassay ......... 334
References ................................................ 335
Questions and Problems .................................... 336
Experiments ................................................... 339
Experiment 1. Data Analysis and Statistical Treatment:
A Case Study on Ozone Concentrations in
Cities of Houston-Galveston Area ............... 340
Experiment 2. Collection and Preservation of Surface Water
and Sediment Samples and Field Measurement
of Several Water Quality Parameters ............ 344
Experiment 3. Gravimetric Analysis of Solids and
Titrimetric Measurement of Alkalinity of
Streams and Lakes .............................. 348
Experiment 4. Determination of Dissolved Oxygen (DO) by
Titrimetric Winkler Method ..................... 352
Experiment 5. Determination of Chemical Oxygen Demand (COD)
in Water and Wastewater ........................ 357
Experiment 6. Determination of Nitrate and Nitrite in Water
by UV-Visible Spectrometry ..................... 362
Experiment 7. Determination of Anionic Surfactant
(Detergent) by Liquid-Liquid Extraction
Followed by Colorimetric Methods ............... 366
Experiment 8. Determination of Hexavalent and Trivalent
Chromium(Cr6+ and Cr3+) in Water by Visible
Spectrometry ................................... 370
Experiment 9. Determination of Greenhouse Gases by Fourier
Transform Infrared Spectrometer ................ 374
Experiment 10. Determination of Metals in Soil-Acid
Digestion and Inductively Coupled Plasma-
Optical Emission Spectroscopy (ICP-OES) ........ 378
Experiment 11. Determination of Explosives Compounds in a
Contaminated Soil by High Performance Liquid
Chromatography (HPLC) .......................... 382
Experiment 12. Measurement of Headspace Chloroethylene by
Gas Chromatography with Flame Ionization
Detector (GC-FID) .............................. 386
Experiment 13. Determination of Chloroethylene by Gas
Chromatography with Electron Capture
Detector (GC-ECD) .............................. 390
Experiment 14. Use of Ion Selective Electrode to Determine
Trace Level of Fluoride in Drinking and
Natural Water .................................. 392
Experiment 15. Identification of BTEX and Chlorobenzene
Compounds by Gas Chromatography-Mass
Spectrometry (GC-MS) ........................... 396
Appendices .................................................... 402
A. Common Abbreviations and Acronyms ......................... 402
B. Structures and Properties of Important Organic
Pollutants ................................................ 407
C1. Standard Normal Cumulative Probabilities .................. 417
C2. Percentiles of t-Distribution ............................. 418
C3. Critical Values for the F-Distribution .................... 419
D. Required Containers, Preservation Techniques, and
Holding Times ............................................. 420
Index ......................................................... 423
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