com Sample Preparation Techniques in Analytical Chemistry Edited by SOMENATH MITRA Department of Chemistry and Environmental Science New Jersey Institute of Technology A JOHN WILEY & SONS, INC.com Sample Preparation Techniques in Analytical Chemistry www.com CHEMICAL ANALYSIS A SERIES OF MONOGRAPHS ON ANALYTICAL CHEMISTRY AND ITS APPLICATIONS Editor J. WINEFORDNER VOLUME 162 A complete list of the titles in this series appears at the end of this volume.com Sample Preparation Techniques in Analytical Chemistry Edited by SOMENATH MITRA Department of Chemistry and Environmental Science New Jersey Institute of Technology A JOHN WILEY & SONS, INC.com Copyright 6 2003 by John Wiley & Sons, Inc. All rights reserved. Published by John Wiley & Sons, Inc., Hoboken, New Jersey.
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Some content that appears in print, however, may not be available in electronic format. Library of Congress Cataloging-in-Publication Data: Sample preparation techniques in analytical chemistry / edited by Somenath Mitra. Chemistry, Analytic—Methodology.S24S26 2003 543—dc21 2003001379 Printed in the United States of America 10 9 8 7 6 5 4 3 2 1 www.com To the hands in the laboratory and the heads seeking information www.com CONTENTS CONTRIBUTORS xvii PREFACE xix CHAPTER 1 SAMPLE PREPARATION: AN ANALYTICAL PERSPECTIVE 1 Somenath Mitra and Roman Brukh 1. The Measurement Process 1 1.
Qualitative and Quantitative Analysis 3 1. Methods of Quantitation 4 1. Errors in Quantitative Analysis: Accuracy and Precision 6 1. Statistical Aspects of Sample Preparation 10 1.
Method Performance and Method Validation 12 1. Range of Quantitation 15 1. Other Important Parameters 15 1. Preservation of Samples 17 1.
Choice of Proper Containers 19 1. Absorption of Gases from the Atmosphere 20 1. Preservation of Unstable Solids 20 vii www.com viii contents 1. Concentration of Sample Extracts 21 1.
Quality Assurance and Quality Control during Sample Preparation 25 1. Determination of Accuracy and Precision 28 1. Contamination Control 32 References 35 SECTION A EXTRACTION AND ENRICHMENT IN SAMPLE PREPARATION CHAPTER 2 PRINCIPLES OF EXTRACTION AND THE EXTRACTION OF SEMIVOLATILE ORGANICS FROM LIQUIDS 37 Martha J. Principles of Extraction 37 2.
Acid–Base Equilibria 50 2. Distribution of Hydrophobic Ionogenic Organic Compounds 57 2. Liquid–Liquid Extraction 57 2. Recent Advances in Techniques 72 2.
Liquid–Solid Extraction 74 2. Solid-Phase Extraction 78 2. Sorbents in SPE 81 2.com contents ix 2. Recent Advances in SPE 113 2.
Solid-Phase Microextraction 113 2. Recent Advances in Techniques 124 2. Stir Bar Sorptive Extraction 125 2. Sorbent and Analyte Recovery 125 2.
Recent Advances in Techniques 129 2. Method Comparison 130 References 131 CHAPTER 3 EXTRACTION OF SEMIVOLATILE ORGANIC COMPOUNDS FROM SOLID MATRICES 139 Dawen Kou and Somenath Mitra 3. Soxhlet and Automated Soxhlet 142 3. Automated Soxhlet Extraction 143 3.
Comparison between Soxtec and Soxhlet 145 3. Selected Applications and Comparison with Soxhlet 147 3. Supercritical Fluid Extraction 148 3. Advantages/Disadvantages and Applications of SFE 154 3.
Accelerated Solvent Extraction 155 www. Advantages and Applications of ASE 161 3. Microwave-Assisted Extraction 163 3. Procedures and Advantages/ Disadvantages 170 3.
Applications of MAE 173 3. Comparison of the Various Extraction Techniques 173 References 178 CHAPTER 4 EXTRACTION OF VOLATILE ORGANIC COMPOUNDS FROM SOLIDS AND LIQUIDS 183 Gregory C. Snow, and Dawen Kou 4. Volatile Organics and Their Analysis 183 4.
Static Headspace Extraction 184 4. Sample Preparation for Static Headspace Extraction 186 4. Optimizing Static Headspace Extraction E‰ciency and Quantitation 187 4. Quantitative Techniques in Static Headspace Extraction 190 4.
Dynamic Headspace Extraction or Purge and Trap 194 4. Operational Procedures in Purge and Trap 199 4. Interfacing Purge and Trap with GC 199 4. Solid-Phase Microextraction 200 www.com contents xi 4.
SPME Method Development for Volatile Organics 201 4. Choosing an SPME Fiber Coating 204 4. Optimizing Extraction Conditions 206 4. Optimizing SPME–GC Injection 207 4.
Liquid–Liquid Extraction with Large- Volume Injection 208 4. Large-Volume GC Injection Techniques 208 4. Liquid–Liquid Extraction for Large-Volume Injection 211 4. Membranes and Membrane Modules 215 4.
Membrane Introduction Mass Spectrometry 217 4. Membrane Extraction with Gas Chromatography 218 4. Optimization of Membrane Extraction 222 4. Conclusions 223 References 223 CHAPTER 5 PREPARATION OF SAMPLES FOR METALS ANALYSIS 227 Barbara B.
Wet Digestion Methods 230 5. Acid Digestion—Wet Ashing 231 5. Comparison of Digestion Methods 235 5. Wet Ashing for Soil Samples 237 5.
Organic Extraction of Metals 241 5. Extraction with Supercritical Fluids 244 5. Ultrasonic Sample Preparation 245 www.com xii contents 5. Solid-Phase Extraction for Preconcentration 245 5.
Sample Preparation for Water Samples 248 5. Preparation of Sample Slurries for Direct AAS Analysis 251 5. Hydride Generation Methods 252 5. Types of Speciation 257 5.
Speciation for Soils and Sediments 258 5. Sequential Schemes for Metals in Soil or Sediment 259 5. Speciation for Metals in Plant Materials 260 5. Speciation of Specific Elements 262 5.
Contamination during Metal Analysis 263 5. Safe Handling of Acids 264 References 264 SECTION B SAMPLE PREPARATION FOR NUCLEIC ACID ANALYSIS CHAPTER 6 SAMPLE PREPARATION IN DNA ANALYSIS 271 Satish Parimoo and Bhama Parimoo 6. DNA and Its Structure 271 6. Physical and Chemical Properties of DNA 274 6.
Isolation of DNA 276 6. Isolation of DNA from Bacteria 278 6. Phenol Extraction and Precipitation of DNA 278 6. Removal of Contaminants from DNA 282 6.
Isolation of Plasmid DNA 283 6. Plasmid DNA Preparation 284 6. Purification of Plasmid DNA 285 6. Genomic DNA Isolation from Yeast 287 www.com contents xiii 6.
DNA from Mammalian Tissues 288 6. Tissues and Tissue Culture Cells 289 6. DNA from Plant Tissue 290 6. Isolation of Very High Molecular Weight DNA 290 6.
DNA Amplification by Polymerase Chain Reaction 291 6. Starting a PCR Reaction 291 6. Isolation of DNA from Small Real- World Samples for PCR 294 6. Assessment of Quality and Quantitation of DNA 296 6.
Precautions for Preparing DNA 296 6. Assessment of Concentration and Quality 296 6. Storage of DNA 299 References 299 CHAPTER 7 SAMPLE PREPARATION IN RNA ANALYSIS 301 Bhama Parimoo and Satish Parimoo 7. RNA: Structure and Properties 301 7.
Types and Location of Various RNAs 303 7. RNA Isolation: Basic Considerations 306 7. Methods of Extraction and Isolation of RNA 307 7. Phenol Extraction and RNA Recovery: Basic Principles 309 7.
Examples of RNA Isolation Using Phenol Extraction 310 7. Guanidinium Salt Method 313 7. Examples of RNA Isolation Using Guanidinium Salts 313 7. Isolation of RNA from Nuclear and Cytoplasmic Cellular Fractions 317 www.com xiv contents 7.
Removal of DNA Contamination from RNA 317 7. Fractionation of RNA Using Chromatography Methods 318 7. Fractionation of Small RNA by HPLC 318 7. mRNA Isolation by A‰nity Chromatography 319 7.
Isolation of RNA from Small Numbers of Cells 323 7. In Vitro Synthesis of RNA 324 7. Assessment of Quality and Quantitation of RNA 326 7. Storage of RNA 328 References 329 CHAPTER 8 TECHNIQUES FOR THE EXTRACTION, ISOLATION, AND PURIFICATION OF NUCLEIC ACIDS 331 Mahesh Karwa and Somenath Mitra 8.
Methods of Cell Lysis 333 8. Mechanical Methods of Cell Lysis 335 8. Nonmechanical Methods of Cell Lysis 339 8. Isolation of Nucleic Acids 342 8.
Solvent Extraction and Precipitation 344 8. Chromatographic Methods for the Purification of Nucleic Acids 346 8. Size-Exclusion Chromatography 347 8. Anion-Exchange Chromatography 348 8.
Solid-Phase Extraction 351 8. A‰nity Purification 352 8. Automated High-Throughput DNA Purification Systems 355 8. Electrophoretic Separation of Nucleic Acids 360 www.com contents xv 8.
Gel Electrophoresis for Nucleic Acids Purification 360 8. Techniques for the Isolation of DNA from Gels 362 8. Capillary Electrophoresis for Sequencing and Sizing 364 8. Microfabricated Devices for Nucleic Acids Analysis 366 8.
Sample Preparation on Microchips 370 References 373 SECTION C SAMPLE PREPARATION IN MICROSCOPY AND SPECTROSCOPY CHAPTER 9 SAMPLE PREPARATION FOR MICROSCOPIC AND SPECTROSCOPIC CHARACTERIZATION OF SOLID SURFACES AND FILMS 377 Sharmila M. Microscopy of Solids 378 9. Spectroscopic Techniques for Solids 381 9. Sample Preparation for Microscopic Evaluation 382 9.
Sectioning and Polishing 382 9. Chemical and Thermal Etching 385 9. Sample Coating Techniques 387 9. Specimen Thinning for TEM Analysis 389 9.
Reactive Ion Techniques 393 9. Chemical Polishing and Electropolishing 394 9. Special Techniques and Variations 399 9. Summary: Sample Preparation for Microscopy 400 www.com xvi contents 9.
Sample Preparation for Surface Spectroscopy 402 9. In Situ Abrasion and Scraping 408 9. In Situ Cleavage or Fracture Stage 408 9. Sample Preparation/Treatment Options for In Situ Reaction Studies 409 9.
Summary: Sample Preparation for Surface Spectroscopy 409 References 410 CHAPTER 10 SURFACE ENHANCEMENT BY SAMPLE AND SUBSTRATE PREPARATION TECHNIQUES IN RAMAN AND INFRARED SPECTROSCOPY 413 Zafar Iqbal 10. Fundamentals of Surface-Enhanced Raman Spectroscopy 415 10. Attenuated Total Reflection Infrared Spectroscopy 420 10. Fundamentals of Surface-Enhanced Infrared Spectroscopy 421 10.
Sample Preparation for SERS 423 10. Vapor Deposition and Chemical Preparation Techniques 424 10. Colloidal Sol Techniques 425 10. Nanoparticle Arrays and Gratings 427 10.
Sample Preparation for SEIRA 431 10. Potential Applications 433 References 436 INDEX 439 www.com CONTRIBUTORS Roman Brukh, Department of Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, NJ 07102 Zafar Iqbal, Department of Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, New Jersey 07102 Mahesh Karwa, Department of Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, NJ 07102 Barbara B. Kebbekus, Department of Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, NJ 07102 Dawen Kou, Department of Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, NJ 07102 Somenath Mitra, Department of Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, NJ 07102 Sharmila M. Mukhopadhyay, Department of Mechanical and Materials Engineering, Wright State University, Dayton, OH 45435 Bhama Parimoo, Department of Pharmaceutical Chemistry, Rutgers University College of Pharmacy, Piscataway, NJ 08854 Satish Parimoo, Aderans Research Institute, Inc., 3701 Market Street, Philadelphia, PA 19104 Gregory C.
Slack, Department of Chemistry, Clarkson University, Potsdam, NY 13676 Nicholas H. Snow, Department of Chemistry and Biochemistry, Seton Hall University, South Orange, NJ 07079 Martha J. Wells, Center for the Management, Utilization and Protection of Water Resources and Department of Chemistry, Tennessee Technological University, Cookeville, TN 38505 xvii www.com PREFACE There has been unprecedented growth in measurement techniques over the last few decades. Instrumentation, such as chromatography, spectroscopy and microscopy, as well as sensors and microdevices, have undergone phe- nomenal developments.
Despite the sophisticated arsenal of analytical tools, complete noninvasive measurements are still not possible in most cases. More often than not, one or more pretreatment steps are necessary.