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 Environmental
Chemical Analysis
Second Edition
 Environmental
Chemical Analysis
Second Edition

Somenath Mitra
Pradyot Patnaik
Barbara B. Kebbekus
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742

© 2019 by Taylor & Francis Group, LLC

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Library of Congress Cataloging-in-Publication Data

Names: Mitra, S. (Somenath), 1959- author. | Patnaik, Pradyot, author. |

Kebbekus, Barbara B., author.
Title: Environmental chemical analysis / S. Mitra, Pradyot Patnaik,
and B.B. Kebbekus.
Description: Second edition. | Boca Raton : CRC Press, [2018] | Previous
edition by B.B. Kebbekus and S. Mitra. | Includes bibliographical references
and index.
Identifiers: LCCN 2018013804| ISBN 9780849338380 (pbk. : alk. paper) |
ISBN 9781138604094 (hardback : alk. paper) | ISBN 9780429458200 (ebook)
Subjects: LCSH: Environmental chemistry. | Pollution--Measurement.
Classification: LCC TD193 .K43 2018 | DDC 577/.14--dc23
LC record available at https://lccn.loc.gov/2018013804

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To our children and the environment they will inherit.
Contents
Preface���������������������������������������������������������������������������������������������������������������xix
Authors���������������������������������������������������������������������������������������������������������������xxi

Chapter 1 Introduction to Environmental Measurements................................. 1

1.1 Role of Measurement in Environmental Studies................... 1
1.1.1 Units of Measurement.............................................. 2
1.1.2 Conversions between Units...................................... 3
1.1.3 Significant Figures................................................... 5
1.2 Pollutants: Sources and Measurements................................. 6
1.2.1 Classes of Environmental Contaminants................. 6
1.2.1.1 Products of Combustion........................... 7
1.2.1.2 Industrial Emissions................................. 7
1.2.1.3 Other Sources of Environmental
Contamination.......................................... 8
1.2.2 Regulating the Environment.................................... 9
1.3 Design of Environmental Studies........................................ 11
1.3.1 Sampling and Analysis........................................... 12
1.4 Basic Statistical Data Handling........................................... 13
1.4.1 Errors in Quantitative Analysis.............................. 13
1.4.2 Statistics of Repeated Measurements: Precision.... 14
1.4.2.1 Precision and Standard Deviation.......... 14
1.4.3 Distribution of Error............................................... 16
1.4.4 Confidence Interval and the t-Distribution............. 18
1.4.4.1 Estimation of Mean from Several
Sets of Measurements............................. 18
1.4.4.2 Estimation of Standard Deviation
from Several Sets of Measurements....... 19
1.5 Significance Tests................................................................ 19
1.5.1 Hypothesis Testing................................................. 19
1.5.1.1 Comparison between a Measured
and a Known Value................................. 20
1.5.1.2 Comparison of the Mean of Two
Samples................................................... 20
1.5.1.3 Comparison of Standard Deviations
Using the F-Test...................................... 22
1.5.2 Outliers................................................................... 24
1.5.2.1 Rule of the Huge Error........................... 24
1.5.2.2 Dixon Test for Rejection of Outliers....... 24
1.5.3 Reporting Data....................................................... 25
1.6 Standards and Calibration................................................... 25
1.6.1 Calibration Methods............................................... 26

vii
viii Contents

1.6.2 Standard Addition Method..................................... 26

1.7 Performance of Analytical Methods: Figures of Merit....... 28
1.7.1 Sensitivity............................................................... 28
1.7.2 Detection Limit...................................................... 29
1.7.3 Range of Quantitation............................................ 30
1.7.4 Validation of New Methods................................... 30
Study Questions.............................................................................. 32

Chapter 2 Environmental Sampling................................................................ 37

2.1 The Sampling Plan.............................................................. 37
2.1.1 Spatial and Temporal Variability........................... 38
2.1.2 Development of the Plan........................................ 39
2.1.3 Sampling Strategies................................................ 40
2.1.3.1 Systematic Sampling.............................. 42
2.1.3.2 Random Sampling.................................. 42
2.1.3.3 Judgmental Sampling............................. 42
2.1.3.4 Stratified Sampling................................. 43
2.1.3.5 Haphazard Sampling.............................. 43
2.1.3.6 Continuous Monitoring........................... 43
2.2 Types of Samples................................................................. 44
2.3 Sampling and Analysis........................................................ 45
2.3.1 Samples in the Laboratory..................................... 46
2.4 Statistical Aspects of Sampling........................................... 47
2.5 Water Sampling................................................................... 49
2.5.1 Surface Water Sampling......................................... 49
2.5.2 Ground Water Well Sampling................................ 51
2.6 Biological Tissue Sampling................................................. 52
2.7 Soil Sampling...................................................................... 52
2.8 Sampling Stratified Levels in Containers............................ 54
2.9 Preservation of Samples...................................................... 55
2.9.1 Volatilization.......................................................... 55
2.9.2 Choice of Proper Containers.................................. 55
2.9.3 Absorption of Gases from the Atmosphere............ 57
2.9.4 Chemical Changes.................................................. 57
2.9.5 Sample Preservation for Soil, Sludges,
and Hazardous Wastes........................................... 57
Study Questions.............................................................................. 58

Chapter 3 Spectroscopic Methods.................................................................. 59

3.1 Spectroscopic Methods for Environmental Analysis.......... 59
3.1.1 Properties of Electromagnetic Radiation............... 59
3.1.2 The Electromagnetic Spectrum.............................. 61
3.1.3 Radiation and Matter.............................................. 62
Contents ix

3.2 Absorption Spectroscopy.................................................... 66

3.2.1 Beer’s Law.............................................................. 66
3.3 Emission Spectroscopy........................................................ 69
3.3.1 Fluorescence........................................................... 70
3.3.2 Atomic Emission.................................................... 71
3.4 Spectroscopic Apparatus..................................................... 72
3.4.1 Light Sources.......................................................... 72
3.4.2 Wavelength Selection............................................. 73
3.4.2.1 Filters...................................................... 73
3.4.2.2 Monochromators..................................... 74
3.4.3 Detectors................................................................ 76
3.5 Ultraviolet and Visible Absorption Spectroscopy............... 76
3.5.1 UV and Visible Instrumentation............................ 78
3.5.1.1 Light Sources.......................................... 78
3.5.1.2 UV–Vis Detectors................................... 78
3.5.1.3 Ultraviolet: Visible Spectroscopy
Samples................................................... 80
3.5.2 Colorimetry............................................................ 80
3.6 Infrared Spectroscopy......................................................... 82
3.6.1 Scanning Infrared Instrumentation........................ 83
3.6.1.1 IR Sources.............................................. 83
3.6.1.2 Infrared Monochromators...................... 84
3.6.2 Fourier Transform Infrared Spectrometry............. 84
3.6.2.1 Advantages of FTIR............................... 87
3.6.2.2 Samples for Infrared Spectroscopy........ 88
3.7 Atomic Absorption Spectroscopy....................................... 91
3.7.1 Flame Atomic Absorbance Spectroscopy.............. 92
3.7.2 Graphite Furnace Atomic Absorption
Spectrometry.......................................................... 94
3.7.3 Interferences in Atomic Absorption....................... 96
3.7.3.1 Spectral Interference............................... 96
3.7.3.2 Chemical Interference............................ 96
3.7.3.3 Ionization Interference............................ 97
3.7.3.4 Background Correction in Atomic
Absorption Spectrometry....................... 97
3.8 Inductively Coupled Plasma Emission Spectroscopy.......... 98
3.8.1 Comparison of Atomic Spectroscopic
Methods................................................................ 100
3.9 X-Ray Fluorescence............................................................101
3.9.1 Wavelength-Dispersive XRF versus Energy-
Dispersive XRF.................................................... 102
3.9.2 X-Ray Instrumentation......................................... 102
3.9.2.1 Sources.................................................. 102
3.9.2.2 X-Ray Detectors................................... 103
3.9.2.3 X-Ray Fluorescence Samples............... 104
x Contents

3.10 Hyphenated Spectroscopic Methods................................. 106

Study Questions............................................................................ 106

Chapter 4 Chromatographic Methods........................................................... 109

4.1 Principles of Chromatography........................................... 109
4.1.1 Column Efficiency.................................................112
4.1.2 The General Elution Problem................................119
4.2 Quantitation in Chromatography........................................119
4.2.1 External Standard Method................................... 120
4.2.2 The Internal Standard Method............................. 120
4.3 Gas Chromatography......................................................... 121
4.3.1 Injection Devices.................................................. 121
4.3.2 Columns............................................................... 123
4.3.2.1 Packed Columns................................... 125
4.3.2.2 Open Tubular Columns......................... 126
4.3.2.3 Column Temperature............................ 128
4.4 GC Detectors..................................................................... 130
4.4.1 Thermal Conductivity Detector............................131
4.4.2 Flame Ionization Detector.................................... 132
4.4.3 Electron Capture Detector.................................... 133
4.4.4 Photoionization Detector...................................... 134
4.4.5 Flame Photometric Detector................................ 135
4.4.6 Pulsed Flame Photometric Detector.................... 136
4.4.7 Thermionic or Nitrogen–Phosphorous
Detector............................................................ 137
4.4.8 Pulsed Discharge Detector................................... 137
4.4.9 Mass Selective Detector....................................... 137
4.4.10 Comparison of Detectors..................................... 138
4.5 High-Performance Liquid Chromatography..................... 138
4.5.1 Reverse Phase Liquid Chromatography............... 139
4.5.2 Normal Phase Liquid Chromatography................141
4.6 HPLC Instrumentation.......................................................141
4.6.1 Solvent Delivery Systems......................................141
4.6.2 Solvent Gradient Systems......................................143
4.6.3 Sample Injectors................................................... 144
4.6.4 HPLC Columns.................................................... 144
4.6.4.1 Precolumns and Guard Columns.......... 144
4.6.4.2 Analytical Columns.............................. 145
4.6.4.3 Eluents.................................................. 146
4.7 HPLC Detectors................................................................ 148
4.7.1 UV Absorption Detectors..................................... 149
4.7.2 Fluorescence Detectors........................................ 151
4.7.3 Evaporative Light Scattering Detector................. 152
4.7.4 Mass Spectrometric Detection............................. 153
Contents xi

4.8 Ion Chromatography.......................................................... 153

4.9 Supercritical Fluid Chromatography................................. 155
4.9.1 SFC Instrumentation............................................ 157
4.10 Applications of Chromatography in Environmental
Analysis............................................................................. 158
Study Questions............................................................................ 159

Chapter 5 Mass Spectrometry........................................................................161

5.1 Interpretation of Spectra.....................................................161
5.2 Basic Instrumentation........................................................ 165
5.2.1 Vacuum System.................................................... 166
5.2.2 Inlet...................................................................... 166
5.3 Ion Sources........................................................................ 167
5.3.1 Electron Impact Ionization................................... 168
5.3.2 Chemical Ionization............................................. 169
5.3.3 Atmospheric Pressure Ionization Sources.............170
5.3.4 Proton Transfer Reaction MS................................171
5.4 Mass Analyzers................................................................. 172
5.4.1 Quadrupole Mass Analyzer...................................173
5.4.2 Magnetic Sector Mass Analyzer...........................174
5.4.3 The Ion Trap Mass Analyzer.................................175
5.5 Ion Detectors......................................................................178
5.6 Gas Chromatography MS.................................................. 179
5.7 Liquid Chromatography MS...............................................181
5.8 Inductively Coupled Plasma MS....................................... 182
5.9 Data Collection.................................................................. 185
5.10 Library Searching Techniques.......................................... 187
Study Questions............................................................................ 189

Chapter 6 Sample Preparation Techniques....................................................191

6.1 Extraction of Organic Analytes from Liquid Samples...... 192
6.1.1 Liquid–Liquid Extraction..................................... 192
6.1.1.1 Successive Extractions.......................... 193
6.1.1.2 Instrumentation for LLE....................... 194
6.1.1.3 Continuous LLE................................... 194
6.1.2 Solid-Phase Extraction......................................... 196
6.1.2.1 The SPE Process................................... 197
6.1.2.2 Advantages of SPE............................... 198
6.1.3 Solid-Phase Microextraction................................ 199
6.2 Extraction of Organic Analytes from Solid Samples........ 199
6.2.1 Soxhlet Extraction................................................ 200
6.2.2 Accelerated Solvent Extraction............................ 201
6.2.3 Ultrasonic Extraction of Organics....................... 203
xii Contents

6.2.4Supercritical Fluid Extraction.............................. 203

6.2.4.1 Instrumentation..................................... 204
6.2.4.2 Choosing SFE Conditions..................... 205
6.2.4.3 Advantages of SFE............................... 205
6.3 Post-Extraction Procedures............................................... 206
6.3.1 Concentration of Sample Extracts........................ 206
6.3.2 Sample Cleanup.................................................... 206
6.4 Extraction of Metals from Sample Matrices..................... 208
6.4.1 Acid Digestion of Samples for Determination
of Metals............................................................... 209
6.4.2 Extraction Procedures.......................................... 209
6.4.3 Microwave Digestion............................................ 209
6.4.4 Ultrasonic Extraction............................................210
6.4.5 Organic Extraction of Metals................................210
6.4.5.1 Formation of Metal Chelates.................210
6.5 Speciation of Metals in Environmental Samples.............. 213
Study Questions............................................................................ 215

Chapter 7 Chemical Methods........................................................................217

7.1 Types of Chemical Reactions.............................................217
7.1.1 Precipitation..........................................................219
7.1.2 Complexation and Chelation Reactions................219
7.1.3 Oxidation/Reduction Reactions........................... 220
7.1.4 Derivatization Reactions...................................... 221
7.1.4.1 Alkylation and Acylation...................... 223
7.1.4.2 Sylilation............................................... 223
7.1.4.3 Diazotization......................................... 224
7.1.4.4 Selection of Derivatizing Reagent........ 224
7.2 Wet Methods...................................................................... 227
7.2.1 Titrations.............................................................. 227
7.2.2 Titration Calculations........................................... 227
7.2.3 Types of Titrations................................................ 229
7.3 Colorimetric Methods....................................................... 231
7.3.1 Colorimetric Indicating Tubes for Air Pollutants.... 232
Study Questions............................................................................ 233
Suggested Reading....................................................................... 233

Chapter 8 Electrochemical Methods............................................................. 235

8.1 Potentiometric Measurements........................................... 235
8.1.1 pH Measurement.................................................. 235
8.1.2 Other Specific Ion Electrodes.............................. 237
8.2 Determination of Metals by Voltammetry........................ 239
Study Questions............................................................................ 241
Contents xiii

Chapter 9 Radiochemical Methods............................................................... 243

9.1 Units of Measurement....................................................... 243
9.2 Instruments for Measuring Radioactivity......................... 244
9.2.1 Gas: Flow Proportional Counters......................... 244
9.2.2 Alpha Scintillation Counter................................. 245
9.2.3 Liquid Scintillation Counters............................... 245
9.2.4 Alpha Spectrometers............................................ 246
9.2.5 Gamma Spectrometers......................................... 246
9.3 Determination of Gross Alpha and Gross Beta
Radioactivity...................................................................... 247
9.3.1 Evaporation Method............................................. 247
9.3.1.1 Gross Activity of the Sample................ 247
9.3.1.2 Activity of Dissolved and
Suspended Matter................................. 248
9.3.1.3 Activity of Semisolid Samples............. 249
9.3.2 Coprecipitation Method for Gross Alpha
Activity................................................................. 250
9.4 Measurement of Specific Radionuclides........................... 251
9.4.1 Radium................................................................. 251
9.4.1.1 Precipitation Method and Alpha
Counting............................................... 252
9.4.1.2 Precipitation and Emanation
Method to Measure Radium as
Radon-222............................................. 252
9.4.1.3 Sequential Precipitation Method.......... 253
9.4.1.4 Measurement of Radium-224 by
Gamma Spectroscopy........................... 254
9.4.2 Radon................................................................... 254
9.4.3 Uranium................................................................ 255
9.4.3.1 Determination of Total Alpha Activity.... 255
9.4.3.2 Determination of Isotopic Content
of Uranium Alpha Activity................... 256
9.4.4 Radioactive Strontium.......................................... 256
9.4.5 Tritium.................................................................. 258
9.4.6 Radioactive Cesium.............................................. 259
Study Questions............................................................................ 260
Suggested Reading....................................................................... 261

Chapter 10 Approaches to the Measurement of Biological Pollutants........... 263

10.1 Introduction....................................................................... 263
10.2 The Microbiological Approach......................................... 263
10.3 Fluorescence Microscope.................................................. 264
10.4 Molecular Biology Techniques.......................................... 266
xiv Contents

10.5 The PCR and the Sequencing Approach........................... 267

10.6 Isolation and Purification of DNA..................................... 268
10.6.1 Example Method for DNA Isolation from
Bacteria Such as E. coli from a Bacterial
Culture.................................................................. 268
10.6.1.1 DNA Amplification by PCR................. 270
10.6.1.2 Gel Electrophoresis............................... 276
10.6.1.3 Fluorescent In Situ Hybridization
and the Analysis of the Single Cell...... 277
10.7 Coliform Groups of Bacteria............................................. 279
10.8 Multiple Tube Fermentation/Most Probable Number
Index Test.......................................................................... 281
10.9 Radiometric Detection of Fecal Coliforms....................... 282
10.10 Bioluminescence Test........................................................ 283
10.11 Seven-Hour Fecal Coliform Test....................................... 283
Study Questions............................................................................ 283
Suggested Reading....................................................................... 284

Chapter 11 Methods for Air Analysis............................................................. 285

11.1 Keeping the Air Clean....................................................... 285
11.2 Determination of Gaseous Species.................................... 286
11.2.1 Carbon Monoxide................................................. 287
11.2.1.1 Carbon Monoxide by Nondispersive
Infrared Absorption.............................. 287
11.2.2 Carbon Dioxide and Carbon Monoxide by
Gas Chromatography........................................... 289
11.2.3 Determination of Sulfur Species.......................... 289
11.2.4 Determination of Nitrogen Oxides in Air............ 290
11.2.5 Determination of Ozone in Air Samples.............. 292
11.2.6 Determination of Radon in Air............................ 292
11.2.6.1 Sampling for Radon.............................. 292
11.2.6.2 Analysis of Samples for Radon............. 293
11.3 Determination of Volatile Organic Compounds............... 294
11.3.1 Adsorbent Trap Sampling.................................... 294
11.3.1.1 Thermal Desorption of VOC
Samples.............................................. 299
11.3.1.2 Solvent Desorption of VOC Samples..... 300
11.3.2 Whole Air Sampling............................................ 301
11.3.2.1 Concentration of Analytes from
Whole Air Samples............................... 303
11.3.3 GC Analysis of VOC............................................ 304
11.3.3.1 Example Determination: VOC in
Ambient Air by Trapping and
Thermal Desorption.............................. 304
Contents xv

11.4 Other Methods for Analysis of Volatiles and Gases......... 306

11.4.1 Determination of Non-Methane Organic
Carbon.................................................................306
11.4.2 Annular Denuder Methods for Air Analysis........ 307
11.4.3 Impinger Methods for Air Sampling.................... 309
11.4.3.1 Colorimetric Indicating Tubes for
Air Pollutants.........................................311
11.5 Determination of Pollutants in Particulate Material..........312
11.5.1 Particle-Size Fractionators....................................314
11.5.2 Filters for Air Sampling........................................315
11.5.2.1 Determination of Total Suspended
Particulates in Air..................................316
11.5.3 Division of Filters..................................................316
11.5.3.1 Determination of Metals in
Airborne Particulates.............................317
11.6 Example Determination: Lead and PAH in airborne
Particulates.........................................................................318
11.6.1 Determination of Anions in Airborne
Particulate..............................................................318
11.6.2 Determination of Organic Species in
Particulate Material...............................................318
11.7 Field Methods for Air Analysis..........................................319
11.8 Methods for Stack Monitoring.......................................... 320
Study Questions............................................................................ 321

Chapter 12 Methods for Water Analysis......................................................... 323

12.1 Sample Collection and Preservation.................................. 324
12.2 Potentiometry for Ions and Gases in Aqueous Solution........ 326
12.3 Metals in Water Samples................................................... 329
12.3.1 Sample Filtration.................................................. 330
12.3.2 Digestion of Metal Samples..................................331
12.3.3 Preconcentrating the Sample.................................331
12.3.4 Separating “Labile” Metal Species...................... 332
12.3.4.1 Atomic Absorption Methods................ 332
12.3.5 Inductively Coupled Plasma Methods.................. 335
12.3.6 Determination of Metals by Voltammetry........... 335
12.3.6.1 Example Determination: Chromium
in Fresh Water....................................... 337
12.4 Inorganic Anions in Water................................................ 338
12.4.1 Ion Chromatographic Analysis for Common
Anions.................................................................. 338
12.5 Organic Compounds in Water........................................... 339
12.5.1 Biochemical Oxygen Demand.............................. 341
12.5.2 Chemical Oxygen Demand.................................. 342
xvi Contents

12.5.3 Total Organic Carbon........................................... 342

12.6 Volatile Organic Compounds in Water............................. 343
12.6.1 Measurement of VOCs Using Purge and Trap........ 343
12.6.2 Head Space Screening for VOCs......................... 346
12.6.3 Screening for VOCs by Solid-Phase
Microextraction.................................................... 347
12.7 Semivolatile Organics in Water......................................... 347
12.7.1 Extractable Base/Neutrals and Acids................... 347
12.7.2 Pesticides.............................................................. 348
12.7.2.1 Example Determination: Haloacetic
Acid and Trichlorophenol in
Drinking Water..................................... 349
12.8 Field Methods for Water.................................................... 350
Study Questions............................................................................ 350

Chapter 13 Methods for Analysis of Solid Samples....................................... 353

13.1 Sampling............................................................................ 354
13.1.1 Preparation of Solid Samples............................... 356
13.2 Measurement of Soil pH.................................................... 357
13.3 Analysis of Metals in Soil and Solids............................... 358
13.3.1 Determination of Mercury................................... 360
13.3.2 Determination of Arsenic and Selenium.............. 360
13.3.3 Example Determination: Simultaneous
Measurement of Metals Such as Pb, Cr, Fe,
Cd, and Ba in Dry Sewage Sludge....................... 360
13.3.4 Analysis of Solids with X-Ray Fluorescence....... 361
13.4 Analysis of Soil for Total Nitrogen.................................... 361
13.5 Colorimetric Tests for Soil and Sludge Analysis............... 361
13.5.1 Determination of Phosphorous............................. 362
13.5.2 Determination of Aluminum................................ 362
13.6 Measurement of Total Organic Carbon in Soil................. 362
13.7 Volatile Organics in Soils or Solids................................... 363
13.7.1 Measurement of VOCs Using Purge and Trap..... 363
13.7.2 Head Space Analysis............................................ 364
13.7.3 Determination of VOC Using SPME................... 365
13.8 Total Petroleum Hydrocarbon in Soil and Sludge............. 365
13.9 Semivolatile Organics in Soil and Sludge......................... 366
13.9.1 Example Determination: Dioxin in a Herbicide....... 366
13.9.2 Organochlorine Pesticides and
Polychlorinated Biphenyls in Solids..................... 369
13.10 Leaching Tests for Wastes................................................. 373
13.11 Immunoassay Tests............................................................ 374
13.12 Field Methods for Solids................................................... 376
Study Questions............................................................................ 376
Contents xvii

Chapter 14 Quality Assurance and Quality Control....................................... 379

14.1 Determination of Accuracy and Precision........................ 381
14.2 Statistical Control.............................................................. 383
14.2.1 Control Charts...................................................... 383
14.2.2 Control Samples................................................... 384
14.2.3 Background or Control Site Samples................... 386
14.3 Performance Evaluation Samples...................................... 387
14.3.1 Preparation of Evaluation Samples...................... 387
14.3.2 Stability of Evaluation Samples........................... 388
14.4 Contamination Control...................................................... 388
14.4.1 Blanks................................................................... 389
14.5 QA for the Example Determinations................................. 391
14.5.1 Determination of VOC in Air by Tenax
Trapping and Thermal Desorption....................... 392
14.5.2 Determination of Haloacetic Acid and
Trichlorophenol in Water..................................... 392
14.5.3 Determination of Metals in Dry Sludge............... 393
Study Questions............................................................................ 394

Chapter 15 New Classes of Emerging Pollutants: Their Classification,

Extractions, and Analysis............................................................. 395
15.1 An Overview..................................................................... 395
15.2 Sample Extractions............................................................ 395
15.3 Analysis............................................................................. 401
15.3.1 Nonionic Surfactants: Alkyl Phenols and
Alkyl Phenol Ethoxylates..................................... 402
15.3.2 Flame Retardants, Plasticizers, and
Lubricants: Organophosphates............................. 402
15.3.3 Pharmaceuticals and Personal Care Products...... 403
15.3.4 Steroids and Hormones........................................ 403
15.3.5 Nanomaterials...................................................... 404
15.3.5.1 Screening and Characterization
of Nanoparticles.................................... 404
15.3.5.2 Separation of Nanoparticles.................. 406
Study Questions............................................................................ 406
Suggested Reading....................................................................... 407

Index.................................................................................................................. 409
Preface
Chemical measurements are fundamental to all environmental and pollution-
related activities. Identification and quantitation of contaminants and pollutants
are necessary before decisions related to the environment can be made or actions
taken. For example, to study the depletion of the ozone layer in the stratosphere,
it is important to measure the concentrations of chlorofluorocarbons in the upper
atmosphere; to understand pesticide contamination, pesticide residues have to be
measured in food, soil, and water; to regulate industrial discharges, contaminant
levels have to be monitored at regular intervals in the effluents. Furthermore, there
are regulatory requisites for the monitoring of pollutants for which understanding
the concepts of environmental analyses is equally important. Therefore, the subject
of the trace environmental analyses has become an integral part of many areas of
environmental science and engineering, industrial hygiene, and pollution control.
This has necessitated the study and training of environmental analyses in colleges
and universities; both at the graduate and undergraduate levels.
The environment is a massive sink where even large quantities of pollutants
are diluted to very low concentrations. Even at these levels, pollutants can be
detrimental to human health and to the biosphere. The environment is made up of a
large number of different chemical species, so the matrix in which the chemicals of
interest must be measured is complex. The combination of low concentrations and
complex matrices makes environmental measurements a challenging task - often
like finding the “needle in the haystack”. Sophisticated analytical instruments
such as chromatographs, mass spectrometers, and atomic spectrometers are used
to measure organic and inorganic components present in concentrations as low
as parts per billion or trillion. It is important to have an understanding of the
principles behind these instruments in order to use them, or even to use the data
produced by them.
This text was developed from our experience in teaching courses in
environmental analysis which have served both graduate and upper-class
undergraduate students majoring in environmental science and engineering,
chemistry, chemical engineering, and geo- and biosciences. The text is intended
for students interested in any aspect of environmental science, and it is expected
that they will come from diverse backgrounds including chemistry, geology,
engineering, and environmental and biological sciences. Consequently, this text
does not assume a background in analytical chemistry. From the spectrum of
available analytical instrumentation, only those widely used in environmental
measurements have been presented. The important topics of sampling, sample
preparation, basic statistics, and the operating principles and descriptions of major
techniques such as spectroscopy, chromatography, and mass spectrometry have
been covered along with quality assurance and control. In the later chapters, the
major environmental matrices, air, water, soils, and solids are explored in more
detail. Within these chapters several “example determinations” are presented.

xix
xx Preface

The first edition of this book has been a success. Upon the advice of many of our
colleagues and students we are bringing out this second edition. Five new chapters
have been incorporated into this edition, which include biological, radiochemical,
electrochemical, and chemical methods including many derivatization reactions,
as well a full chapter on the emerging contaminants. Finally, we have attempted
to make this text sufficiently complete so that the reader will come away with
enough information to develop an insight into chemical analysis associated with
the environment.
Authors
Somenath Mitra is currently the Distinguished Professor of Chemistry and
Environmental Science and the Executive Director of Otto York Center for
Environmental Engineering and Science at the New Jersey Institute of Technology.
He has published extensively in peer-reviewed journals in multiple areas including
Analytical Chemistry, Environmental Science and Nanotechnology. He is the
editor of popular text “Sample Preparation Techniques in Analytical Chemistry”
(John Wiley and Sons). He has also received several awards for his scientific
accomplishments.

Pradyot Patnaik is currently an Adjunct Professor at the New Jersey Institute

of Technology and also teaches at the Community College of Philadelphia.
Earlier, he served as the Laboratory Director at the Interstate Environmental
Commission, New York and a researcher at the Center for Environmental Science,
City University of New York, at the College of Staten Island. He is also the author
of the books, “A Comprehensive Guide to the Hazardous Properties of Chemical
Substances”, “Handbook of Environmental Analysis”, “Handbook of Inorganic
Chemicals” and “Dean’s Analytical Chemistry Handbook”.

Professor Barbara B. Kebbekus was formerly the Chairperson in the Department

of Chemical Engineering, Chemistry and Environmental Science at the New
Jersey Institute of Technology and authored several research papers in topics such
as environmental and analytical chemistry.

xxi
 1 Introduction to
Environmental
Measurements
The entire world is the environmental scientist’s laboratory. Environmental
science takes for its own the study of the composition of the atmosphere, water,
soil, and how materials are taken up and given back by plants and animals. It
examines the transport of various chemical species, elements, and compounds,
among the atmosphere, the hydrosphere, the geosphere, and the biosphere. Of great
importance in the development of this branch of science has been the realization
that human activities are having an increasing effect, frequently not for the better,
on the natural environment.
Deterioration of the environment reached significant levels with the dramatic
increase in human population, accompanied by industrialization, which took place
over the past century or so. Major problems brought about by these changes are
the pollution of air, water, and soil; growth in the amount of hazardous waste;
depletion of arable land, energy, and other natural resources; increased exposure
to toxic chemicals in food, water, and air; and exposure to radiation. It was not
until the 1960s that an awareness of these problems grew all over the world. Since
then, a plethora of environmental regulations have been promulgated to protect
our environment.

1.1 ROLE OF MEASUREMENT IN ENVIRONMENTAL STUDIES

All environmental studies ultimately depend on the results of chemical analysis
of samples of air, water, soil, and biological organisms. Policies on reduction of
pollution cannot be designed if the extent and identity of the pollutants is not
known. Emissions cannot be regulated if there is no accurate and reliable method
of monitoring the emitted materials. The source of such problems as global climate
change can only be determined with accuracy by monitoring the concentrations of
the various greenhouse gases in the atmosphere over long periods of time and at
many locations, and correlating these measurements with observed temperature
trends. The mathematical models constructed to predict the effect on global
climate of changes in atmospheric composition are most reliable when they are
tested against actual data.
Natural cycles cannot be understood if chemical compounds cannot be followed
as they are passed on from air to water to soil and to the biosphere. The analytical
chemist who specializes in the analysis of environmental samples is choosing to

1
2 Environmental Chemical Analysis

work on some of the most challenging problems in analysis, because the analytes
are often present in extremely low quantities, and the matrix can be very complex.
To further add to the problem, the material to be sampled is usually very non-
homogeneous. The sampling of an area such as a landfill, or a constantly changing
system such as a river or the ambient atmosphere requires much thought about
what is to be determined and where and when samples are to be taken.
The environmental scientist or engineer may not be the person who actually
does the laboratory analysis, but he or she may well be the person who specifies
what samples are taken and where, and which analyses should be performed. In
addition, the decisions about how the laboratory data are to be interpreted and what
conclusions can be legitimately drawn are also functions of the environmental
specialist.

1.1.1 Units of Measurement

When environmental samples are analyzed, the units in which the results are
expressed vary with the type of sample. Concentrations are expressed in SI units,
such as mL/m3 or µg/kg. However, data are sometimes expressed as parts per
million (ppm) or parts per billion (ppb). For gases, ppm can be defined as moles
of analyte per million (106) moles of air, or volume of analyte per million volumes
of air. Moles of analyte per 109 moles of sample define ppb. The equivalent SI
units are mL/m3 for ppm and µL/m3 for ppb. Since at any given temperature and
pressure the number of moles of gas occupying a certain volume is the same for
all gases, these two definitions are equivalent. Only in cases where the ideal gas
law is not valid (i.e., at cryogenic temperatures and high pressures), would this not
be a reasonable assumption. Since most environmental work involves moderate
temperatures and pressures, the assumption is appropriate. For particulate matter
in air, the results are usually expressed as milligrams or micrograms of analyte
per cubic meter of air.
In water analysis, ppm usually implies grams of analyte per million grams
of water. For water, this is equivalent to milligrams of analyte per liter of water.
Remember that this equivalence between ppm and mg/L is valid only for water,
because it is derived from the fact that 1 L of water weighs 1000 g. Table 1.1 lists
some of the more common units of measurement.
In general, it is preferable to use the SI units when reporting concentrations.
When ppm or ppb are used, ambiguity about the basis of the notation can be
eliminated by using a more specific notation (e.g., ppmw or ppbv) to indicate that
the concentration is given in weight/weight or volume/volume terms. However,
µg/L or µg/g are less prone to misinterpretation, and are the international standard.
Very low concentrations are given as µg/kg or parts per trillion, and high
concentrations may reach the percent range. The magnitude of the units should
be chosen so that they are suitable to the amount being reported, although there
may be a reason to report 7000 µg/kg instead of 7 µg/g. If one is comparing,
for example, a series of samples which are all in the µg/kg range except for a
few in the low µg/g range, it would be better to keep the same units for all. It is
Introduction to Environmental Measurements 3

TABLE 1.1
Commonly Used Units of Measurement
Unit Meaning Usual Use

µg/g Micrograms of analyte per gram of sample Concentrations in solid samples

µg/m3 Micrograms of analyte per 1000 L of sample
µL/L Microliter of analyte per liter of sample
ppmv Volumes (or moles) of analyte per 106
Volumes (or moles) of sample
ppmw Grams of analyte per 106 g of sample
ppbw Grams of analyte per 109 g of sample
Concentrations of particulate matter in air
Concentration of liquid analyte in liquid
sample
Concentration of gaseous analyte in air or
other gases
Solid or liquid analyte in solid samples
Solid or liquid analyte in solid samples

simpler to compare data if they are all reported in the same units. On the other
hand, one should avoid trying to make data more eye catching by reporting them
in inappropriate units. One person’s “enormous concentration of 5000 nL/m3 of
benzene in air” may be another’s “bare trace at 0.005 mL/m3” (or even “a half
of a millionth of a percent”!). None of these is incorrect, but an unbiased analyst
would report the 5 µL/m3 concentration, in the most appropriate units, and let the
number speak for itself.

1.1.2 Conversions between Units

Calculations usually have to be done on measurement data to bring these to
a useable form. If the units in which the quantities are expressed are handled
carefully, the calculations are not difficult. In a simple case, the instrument
signal is converted into a quantity of analyte in some quantity of sample,
which is then converted to ppm in the original sample taken in the field. If
the sample has been diluted before analysis, this must be taken into account
in these calculations. The most systematic and error-free way to go about unit
conversion problems is by the factor label method. The basis of this method of
setting up calculations is that multiplication of any quantity by unity does not
change its value. If a number of grams is multiplied by the quantity 1000 mg/g,
the original value does not change, since 1000 mg = 1 g and therefore the
conversion factor is equal to unity. Only the units in which it was expressed have
changed. This is always true if the conversion factor is made up of a numerator
and denominator which are equivalent to each other. If the calculation is written
down with all the factors carefully labeled, and if the factors cancel, leaving the
answer in the correct units, there is little chance of error. One must be careful
that the conversion factors are truly equivalent to unity, and that the labels are
sufficiently detailed so that you do not cancel “grams of sample” with “grams
of benzene” simply because both were labeled “g.” Some useful conversion
factors are found in Table 1.2.
A few examples will review the method.
4 Environmental Chemical Analysis

TABLE 1.2
Some Useful Conversion Factors
1 kilometer (km) 103 meters (m)
1m 103 millimeter (mm)
1m 106 micrometer (µm)
1m 109 nanometer (nm)
1m 100 centimeter (cm)
1 inch (in.) 2.54 cm
1 mile (mi) 5280 ft
1 Liter (L) 1.057 quart (qt)
1 kilogram (kg) 0.4536 pound (lb)
1 cubic meter 35.336 cubic feet

EXAMPLE 1.1
Toluene is trapped from water in a cartridge, eluted with a suitable solvent, and
analyzed by liquid chromatography. A 500 mL portion of sample was used, and
10 mL of reagent used to wash out the trapped toluene. From the analysis, the
10 mL reagent solution was found to contain 5 µg toluene/mL. What was the
concentration of toluene in the original sample?

5 µg toluene 10 mL reagent
× = 50 µg toluene in the sample
1mL reagent

50 µg toluene 1mL water

× = 0.1 µg/g in the original sample
500 mL water 1g water

EXAMPLE 1.2
Particulate matter is filtered from air. After the sample is collected for 8.00 hours
at a flow of 10.0 cfm (cubic feet per minute), the filter is extracted into 100 mL
of solution. The solution is found to contain 23.3 ng/mL of lead. What is the
concentration in the air in ng/m3.
First, calculate the number of cubic meters of air collected:

60 min 10.0 ft 3 1m3

8.00 hours × × × = 135 m3
1hr min 35.3 ft 3

Then calculate the amount of lead in the sample:

23.3ngPb 1mg
× × 100 mL solution = 2.33 × 10−3 mgPb
mL solution 106 ng
Introduction to Environmental Measurements 5

Finally, calculate the concentration in the original air sample:

2.33 × 10−3 mgPb 106 ng ng

3
× = 17.3 3
135 m 1mg m

1.1.3 Significant Figures
The way a measurement is reported says something about the accuracy with which
the measurement was made. If the mass of an object is reported as “1 gram” it
is assumed that the measurement was made fairly roughly. However, if the
reported mass is given as 1.0345 g, one immediately supposes that the object was
weighed carefully on an analytical balance. Therefore, if values are calculated
from measured quantities, it is important to keep the proper number of significant
figures, so that the reader is not misled into thinking that a measurement was done
more carefully than it was. For instance, one might prepare a solution by weighing
out 1.0435 g of sodium chloride into a 100.00 mL volumetric flask and diluting it
to the mark. This gives a solution containing 1.0435 g/100 mL, or 0.010435 g/­mL
or 10.435 mg/mL. Each of the measurements, the volume of solution, and the
mass of sodium chloride, were done to the same accuracy, five significant figures
in both cases, so the final calculated concentration can be legitimately reported
to five significant figures. If 1/4 of the sample is withdrawn using a calibrated
pipet of volume 25.01 mL, and this portion is diluted to 100.00 mL, the resulting
solution is about 1/4 the concentration of the original. A calculator will report that
10.435 mg/mL × (25.01 mL/100.00 mL) is 2.6097935 mg/mL. These are obviously
more figures than are actually significant, and the number should be rounded to
2.610 mg/mL, keeping the four significant figures of the least precisely known piece
of data involved, the volume of the nominally 25 mL pipet (25.01 mL).
The rules are:

• Zeros at the end of a number are usually significant. (Numbers such as

1000 are ambiguous and should be avoided. If four significant figures
are intended, use 1.000 × 103. If only two are intended, use 1.0 × 103.)
• Zeros before a number are not significant. 0.00034 has only 2 significant
figures.
• When numbers are multiplied or divided, the one with the fewest
significant figures will govern the final answer. 1.234 × .0032 = 0.0039.
• When numbers are added or subtracted, the one with the smallest absolute
accuracy will govern the final answer. Adding 123.44 + 2.9177 + 3243.1
gives 3369.4577. This is rounded to one decimal place, 3369.5, as the
third number had only one decimal place.
• Counted numbers, as opposed to measured numbers are assumed to have
as many significant figures as needed in any calculation. This includes
such quantities as 60 min in an hour, or 1000 mm in a meter.
6 Environmental Chemical Analysis

1.2 POLLUTANTS: SOURCES AND MEASUREMENTS

The atmosphere contains just few major constituents: nitrogen (79%), oxygen
(20%), argon (0.9%), carbon dioxide (290–500 µl/L), and water vapor, which
varies widely. However, if we look at materials found in the low µl/L and µl/m3
concentration ranges, there are hundreds of compounds present in air. These are
classified in several ways: gases and particulates, organics and inorganics, toxic
and nontoxic materials. Water samples, likewise have a wide variety of compounds
present, both in dissolved and suspended forms. These vary even more widely
than air samples, as natural waters can contain many substances at quite high
concentrations. Think of spring water, sea water, and sulfur hot springs waters,
all of which are natural, yet have very different compositions. In addition, polluted
waters may have a vast number of anthropogenic materials in them.
Soils and biological materials are even more complex, since their basic matrix
is not simple, as air and water are. Normal plant and animal tissues or even
soil contain a large array of materials and organisms which are necessary to
their normal functioning. Added to this complex matrix may be extraneous
compounds accumulated from the environment. These may be present at levels
which are obviously harmful or they may be low concentrations of materials
which have been shown to be harmful at much higher levels. Or they may be
totally innocuous.
It is at this point where politics and science must fight their major battles. It
may be easy to say that any amount of a harmful compound in, for instance,
human tissues is undesirable and that regulations should be written to prevent this
contamination. This is overly simplistic, however, since modern analytical methods
are often so sensitive that some compounds may be detected at concentrations
below 1 µg/kg. Unfortunately, it is at this very point that it is most difficult to make
valid scientific judgments about the degree of harm any particular exposure will
do. When an exposure causes a verifiable problem for one in a hundred thousand
people, it will be exceedingly difficult to prove.
Results of animal testing are often extrapolated to determine which substances
are harmful and to decide what exposure levels are acceptable. This is inherently
risky, because it has been found that, even between similar species, the
susceptibility to different compounds is widely different. Therefore, extrapolations
from mice to humans cannot be taken as having a strong scientific grounding.
However, it is also not morally acceptable to experiment on controlled groups of
humans, so regulations do not always have the kind of scientific grounding we
would like to see. Most commonly, regulations are based on a combination of
scientific evidence of harm in animal experiments, epidemiological data, informed
judgment, guesswork, and political interests.

1.2.1 Classes of Environmental Contaminants

The term contaminant refers to a material which is present in a part of the
environment where it is not expected. When the material begins to cause a problem,
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