Solid-Phase Extraction Principles and Practice

by Thurman, E. Michael; Mills, M. S.

• ISBN13: 9780471614227
• ISBN10: 047161422X
• Edition: 1st
• Format: Hardcover
• Copyright: 1998-03-16
• Publisher: Wiley-Interscience

Summary

Divided into three main parts, the book begins with a clear explanation of basic SPE conceptsincluding theory, chemistry, and mechanisms of interaction as well as methods development, troubleshooting, and optimization. The next section presents an in-depth look at SPE applications, with separate chapters devoted to clinical, environmental, and natural product chemistry. Numerous examples drawn from each of these three areas illustrate SPE in action in the real world, successfully bridging the gap between principles and practice.The final section of this book discusses the latest SPE technology, with detailed coverage of the automation process, solid-phase extraction disks, and innovations such as solid-phase microextraction and small-volume solid-phase extraction. Suggested reading and references are included throughout, providing a useful springboard for further research and study.Whether you are new to SPE or are looking to keep abreast of the newest developments in SPE methods and uses, Solid-Phase Extraction gives you instant access to the information you needan essential companion for chemists of all types who use SPE in their work.Complete coverage of SPE concepts and applicationsat your fingertips Solid-Phase Extraction (SPE) equips chemists in any field with an incomparable one-stop source of up-to-date information on SPE. With sections devoted to fundamental principles, applications, and new technology, it is both comprehensive and easy to use the ideal working reference on this important subject. Presents a straightforward examination of SPE theory, methods development, chemistry, and mechanisms of interaction Provides detailed coverage of SPE applications in clinical, environmental, and natural product chemistry Features practical examples illustrating a range of real-world SPE uses Prepares chemists to make informed decisions on sorbent selection Covers the latest SPE technology, with valuable insights on automation and new sample preparation methods Offers suggestions for further reading, Internet resources, and product guides

Author Biography

E. M. THURMAN is an organic geochemist at the U.S. Geological Survey with twenty years of research experience in the environmental chemistry of water and soil, as well as extensive experience in sorption chromatography and XAD and SPE resin technology. Dr. Thurman has published research papers on the theory of XAD resins, applications of SPE in environmental chemistry, drug applications of SPE, and isolation of natural products by SPE and ion exchange. He is the coauthor of Immunochemical Technology for Environmental Applications, the coeditor of Herbicide Metabolites in Surface Water and Groundwater, and has written over 80 journal articles on environmental analytical chemistry. gt;M. S. MILLS is a research envi-ronmental chemist with Zeneca Agrochemicals at the Jealott's Hill Research Station, Bracknell, U.K. Dr. Mills was formerly employed by the U.S. Geological Survey in Lawrence, Kansas, where her research interests included exploring the mechanisms and applications of solid-phase extraction in environmental chemistry, investigating the organic geochemistry of naturally occurring aquatic foams, and the degradation and transport of xenobiotics in the vadose zone. She has contributed numerous publications and oral presentations on these topics over the past five years, and was cofounder and co-lecturer of the American Chemical Society short course, "Solid-Phase Extraction in Environmental and Clinical Chemistry." Current research project foci include the degradation and transport of xenobiotics in the vadose zone using radiolabeled techniques and the degradation of xenobiotics in the saturated zone.

Table of Contents

Preface	xvii	(2)
Acknowledgments	xix	(2)
Cumulative Listing of Volumes in Series	xxi
CHAPTER 1 OVERVIEW OF SOLID-PHASE EXTRACTION	1	(24)
1.1. What is Solid-Phase Extraction?	1	(1)
1.2. How to do Solid-Phase Extraction	2	(2)
1.3. Columns and Apparatus for Solid-Phase Extraction	4	(5)
1.4. Sorbents and Modes of Interaction	9	(4)
1.5. Applications of Solid-Phase Extraction	13	(3)
1.6. Automation of Solid-Phase Extraction	16	(1)
1.7. Manufacturers and Bibliographies	17	(2)
1.8. History and Future of Solid-Phase Extraction	19	(3)
Suggested Reading	22	(1)
References	22	(3)
CHAPTER 2 THEORY OF SORPTION AND ISOLATION	25	(26)
2.1. Introduction	25	(1)
2.2. Synthesis of Sorbents	25	(13)
2.2.1. The Silica Particle	25	(4)
2.2.2. Bonded Phases	29	(7)
2.2.3. Polymeric Sorbents	36	(2)
2.3. Mechanisms of Sorption	38	(7)
2.3.1. Reversed Phase	38	(1)
2.3.2. Normal Phase	39	(3)
2.3.3. Ion Exchange	42	(2)
2.3.4. Mixed Mode	44	(1)
2.4. Elution of Sorbents in Solid-Phase Extraction	45	(3)
2.4.1. Reversed Phase	45	(2)
2.4.2. Normal Phase	47	(1)
2.4.3. Ion Exchange and Mixed Mode	48	(1)
Suggested Reading	48	(1)
References	49	(2)
CHAPTER 3 METHODS DEVELOPMENT	51	(20)
3.1. Six-Step Approach to Methods Development	51	(11)
3.1.1. What is Solute Structure? The Clue to Effective Solid-Phase Extraction	51	(1)
3.1.2. Identify the Goal	52	(1)
3.1.3. Obtain Physical Constants	52	(2)
3.1.4. Choose the Mechanism of Solid-Phase Extraction	54	(2)
3.1.5. Elute the Solid-Phase Extraction Sorbent	56	(4)
3.1.6. Perform the Sorption Experiment and Determine Breakthrough	60	(2)
3.2. Executing the Solid-Phase Extraction Experiment in Five Steps	62	(2)
3.2.1. Step 1	63	(1)
3.2.2. Step 2	63	(1)
3.2.3. Step 3	63	(1)
3.2.4. Step 4	64	(1)
3.2.5. Step 5	64	(1)
3.3. Troubleshooting and Optimizing a Method	64	(3)
3.3.1. Problem 1: Incomplete Elution	64	(1)
3.3.2. Problem 2: Breakthrough of Analyte	65	(1)
3.3.3. Problem 3: Significant Breakthrough of Analyte	65	(1)
3.3.4. Problem 4: Interfering Substances	66	(1)
3.4. Critically Evaluate Previously Published Methods	67	(2)
3.5. Simple Summary of Methods Development	69	(1)
Suggested Reading	69	(1)
References	69	(2)
CHAPTER 4 REVERSED-PHASE SOLID-PHASE EXTRACTION	71	(34)
4.1. Introduction	71	(1)
4.2. Structure of Reversed-Phase Sorbents	72	(5)
4.3. Reversed Phase as a Partitioning Mechanism	77	(3)
4.4. Chromatographic Plate Theory and Reversed-Phase Solid-Phase Extraction	80	(8)
4.4.1. Introduction	80	(3)
4.4.2. Theoretical Aspects of Plate Theory	83	(5)
4.5. Chromatographic Plate Theory: Its Application to Reversed-Phase Solid-Phase Extraction	88	(11)
4.5.1. Introduction	88	(4)
4.5.2. Determining and Predicting Breakthrough Volumes	92	(2)
4.5.3. Polarity and Breakthrough	94	(1)
4.5.4. Example Calculation of Breakthrough Volume using k'(w)	95	(1)
4.5.5. Practical Effects of Plate Number on Solid-Phase Extraction	96	(3)
4.6. Examples of Methods Development with Reversed-Phase Solid-Phase Extraction	99	(4)
4.6.1. Trace Enrichment of Pesticides from Groundwater	99	(1)
4.6.2. Extraction of Protein from Dilute Aqueous Solution	100	(1)
4.6.3. Extraction and Purification of Synthetic Oligonucleotides	101	(1)
4.6.4. Extraction of Indole-3-Acetic Acid	102	(1)
4.6.5. Extraction of Catecholamines from Urine	102	(1)
Suggested Reading	103	(1)
References	104	(1)
CHAPTER 5 NORMAL-PHASE SOLID-PHASE EXTRACTION	105	(18)
5.1. Introduction	105	(1)
5.2. Structure and Sorption of Normal-Phase Sorbents	106	(5)
5.3. Elution of Normal-Phase Sorbents	111	(1)
5.4. Examples of Methods Development with Normal-Phase Solid-Phase Extraction	112	(9)
5.4.1. Extraction of Aromatic Hydrocarbons from Crude Oil	113	(1)
5.4.2. Extraction of Polychlorinated Biphenyls from Transformer Oil	114	(1)
5.4.3. Extraction of Carotenes from Plant Tissue	115	(1)
5.4.4. Extraction of N-Nitrosoamine (N-Nitrosopyrrolidine) from Bacon	116	(1)
5.4.5. Extraction of Aflatoxins from Corn, Peanuts, and Peanut Butter	117	(1)
5.4.6. Extraction of Pyridonecarboxylic-Acid Antibacterials from Fish Tissue	118	(1)
5.4.7. Extraction of Vitamin D from Serum	119	(1)
5.4.8. Extraction of Antibiotics from Ointment	120	(1)
Suggested Reading	121	(1)
References	121	(2)
CHAPTER 6 ION-EXCHANGE SOLID-PHASE EXTRACTION	123	(38)
6.1. Introduction	123	(3)
6.2. Structure of Solid-Phase Extraction Ion-Exchanger Sorbents	126	(6)
6.2.1. Cartridges	126	(5)
6.2.2. Disks	131	(1)
6.3. Ion Exchange as a Chemical Reaction	132	(1)
6.4. Selectivity of Ion Exchange	132	(3)
6.5. Donnan Membrane Theory	135	(4)
6.6. Law of Chemical Equilibrium and Selectivity Coefficients	139	(2)
6.7. Kinetics of Ion Exchange	141	(1)
6.8. Methods Development: General Principles	141	(5)
6.8.1. Selecting Cation or Anion Exchange	142	(2)
6.8.2. Molecular Size and Weight	144	(1)
6.8.3. Interferences and Competing Ions	145	(1)
6.9. Methods Development Experiment	146	(1)
6.10. General Method for Ion-Exchange Solid-Phase Extraction	147	(1)
6.11. Examples Using Ion-Exchange Solid-Phase Extraction	148	(11)
6.11.1. Salt Conversions	148	(1)
6.11.2. Preparation of Deionized Water	149	(1)
6.11.3. Isolation of Metal Cations	150	(1)
6.11.4. Isolation of Triazine Herbicides from Soil	151	(1)
6.11.5. Purification of Organic Compounds	152	(2)
6.11.6. Hydroxyatrazine Metabolites from Water	154	(1)
6.11.7. Paraquat and Diaquat in Water	155	(1)
6.11.8. Food and Beverage	155	(1)
6.11.9. Food and Feeds	156	(1)
6.11.10. Pharmaceutical and Biological Applications	157	(1)
6.11.11. Extraction of Cimetidine from Urine	157	(1)
6.11.12. Dacthal Isolation and Derivatization	158	(1)
Suggested Reading	159	(1)
References	159	(2)
CHAPTER 7 ENVIRONMENTAL ANALYSIS	161	(36)
7.1. Structure and Chemistry of Micropollutants	161	(2)
7.2. Generic Approach to Environmental Solid-Phase Extraction	163	(1)
7.3. Water Samples and Trace Enrichment	164	(4)
7.3.1. Introduction	164	(2)
7.3.2. Removal of Interferences	166	(1)
7.3.3. Generic Eluents	167	(1)
7.4. Environmental Protection Agency Methods	168	(4)
7.4.1. Cartridge Methods	168	(2)
7.4.2. Disk Methods	170	(2)
7.5. On-line Solid-Phase Extraction--High-Pressure Liquid Chromatography: Environmental Applications	172	(1)
7.6. Large-Volume Analysis by Solid-Phase Extraction	173	(2)
7.7. Soil Analysis and Solid-Phase Extraction	175	(3)
7.7.1. Solid-Phase Extraction Cleanup	175	(1)
7.7.2. Trace Enrichment	176	(1)
7.7.3. Normal-Phase Solid-Phase Extraction of Soil Extracts	177	(1)
7.8. Air Analysis and Solid-Phase Extraction	178	(2)
7.9. Oil and Grease Analysis	180	(1)
7.10. Examples of Environmental Solid-Phase Extraction	180	(13)
7.10.1. Organochlorine Pesticides in Water	180	(2)
7.10.2. Organochlorine Pesticides in Soil and Sediment	182	(1)
7.10.3. Polyaromatic Hydrocarbons in Water and Soil	182	(2)
7.10.4. Nonionic Herbicides in Water and Soil	184	(1)
7.10.5. Organophosphorus Pesticides in Water and Soil	185	(2)
7.10.6. Nonvolatile Organic Compounds: Carbamates, Substituted Amides, and Phenylureas in Water and Soil	187	(1)
7.10.7. Herbicide Metabolites in Water and Soil	188	(1)
7.10.8. Phenols and Chlorinated Phenols in Water and Soil	189	(2)
7.10.9. Acid Herbicides (2,4-D, 2,4,5-T, Dicamba) and Sulfourea Herbicides in Water and Soil	191	(1)
7.10.10. Anionic Surfactants in Water and Soil	192	(1)
Suggested Reading	193	(1)
References	194	(3)
CHAPTER 8 DRUGS AND PHARMACEUTICALS	197	(26)
8.1. Introduction	197	(1)
8.2. Structure and Chemistry of Drugs	197	(1)
8.3. Sample Matrix	198	(2)
8.4. Mixed-Mode Sorbents	200	(3)
8.5. Application of Mixed Mode	203	(1)
8.6. Sorbents for Drug Analysis	204	(1)
8.7. NIDA Drugs of Abuse	204	(5)
8.7.1. Marijuana	204	(2)
8.7.2. Cocaine	206	(1)
8.7.3. Phencyclidine	206	(1)
8.7.4. Amphetamines	207	(1)
8.7.5. Opiates	208	(1)
8.8. General Drug Analysis and Methods	209	(1)
8.9. Veterinary Applications	209	(1)
8.10. Examples of Methods for Pharmaceutical and Biological Analysis	209	(5)
8.10.1. Cyclosporine in Blood	210	(1)
8.10.2. Vitamin D in Serum	211	(1)
8.10.3. Lipids from Serum and Tissue	212	(1)
8.10.4. Vitamin B(12) in Urine or Aqueous Solution	213	(1)
8.11. Automation and On-line Solid-Phase Extraction for Drug Analysis	214	(1)
8.12. Disk Technology and Drug Analysis	215	(3)
8.13. Innovations in Solid-Phase Extraction for Drug Analysis	218	(1)
Suggested Reading	218	(2)
References	220	(3)
CHAPTER 9 FOOD AND NATURAL PRODUCTS	223	(20)
9.1. Liquefying and Extraction of Food Products	223	(5)
9.1.1. Sample Preparation	223	(4)
9.1.2. Choosing an Extraction Solvent	227	(1)
9.2. Removing Matrix Interferences in Foods	228	(1)
9.2.1. Fats, Oils, and Lipids	228	(1)
9.2.2. Proteins and Meat	228	(1)
9.2.3. Carbohydrates, Polysaccharides, and Salts	228	(1)
9.2.4. Beverages	229	(1)
9.3. Examples of Analyte Isolation from Food Using Solid-Phase Extraction	229	(12)
9.3.1. Atrazine from Corn Oil	229	(1)
9.3.2. Beverages: Organic Acids and Anthocyanins from Wine	230	(2)
9.3.3. Tetracycline Antibiotics in Meat	232	(1)
9.3.4. Fumonisin B(1) in Rodent Feed	233	(2)
9.3.5. Vitamin K(1) in Food	235	(1)
9.3.6. Alpha-Tomatine in Tomatoes	236	(1)
9.3.7. Wine Flavor Components	237	(1)
9.3.8. Solid-Phase Microextraction for Flavor Analysis	237	(1)
9.3.9. Geosmin in Catfish	238	(2)
9.3.10. Folic Acid in Cabbage	240	(1)
Suggested Reading	241	(1)
References	241	(2)
CHAPTER 10 AUTOMATION OF SOLID-PHASE EXTRACTION	243	(38)
10.1. Why Automate Solid-Phase Extraction?	243	(1)
10.2. Automation Equipment	244	(22)
10.2.1. Semiautomated Solid-Phase Extraction	245	(1)
10.2.2. Workstations	246	(18)
10.2.3. Total Automation	264	(2)
10.3. Automating a Manual Solid-Phase Extraction Method	266	(1)
10.4. Process of Automation	266	(6)
10.4.1. The Initial Experiment	266	(1)
10.4.2. Minimize Interferences	267	(1)
10.4.3. Optimize Recovery	268	(1)
10.4.4. Column Drying	269	(1)
10.4.5. Reduce Carryover	270	(1)
10.4.6. Optimize Throughput	271	(1)
10.5. Examples of Automated Solid-Phase Extraction	272	(5)
10.5.1. Phenylurea Herbicides in Water	272	(2)
10.5.2. Triazine Herbicides in Water	274	(3)
10.5.3. Cocaine in Urine	277	(1)
10.6. Conclusions	277	(1)
Suggested Reading	278	(1)
References	279	(2)
CHAPTER 11 SOLID-PHASE EXTRACTION DISKS	281	(22)
11.1. Introduction	281	(1)
11.2. "Free" Disk Format	282	(5)
11.2.1. Empore Disk	282	(2)
11.2.2. SPEC Disc	284	(1)
11.2.3. Speedisk	285	(1)
11.2.4. Novo-Clean Disk	286	(1)
11.2.5. MemSep	287	(1)
11.3. Syringe Disk Format	287	(1)
11.4. How to Use a Solid-Phase Extraction Disk	288	(3)
11.4.1. Manifold and Hardware for Disk Extraction	288	(3)
11.5. Disk Automation	291	(2)
11.6. Examples of Disk Methods	293	(2)
11.6.1. Polynuclear Aromatic Hydrocarbons from Water	293	(1)
11.6.2. Extraction of Polychlorinated Biphenyls from Water	293	(1)
11.6.3. EPA Method 552.1: Haloacetic Acids and Dalapon in Drinking Water	294	(1)
11.6.4. References for Further Environmental Methods Development	294	(1)
11.7. Theory of Disk Operation	295	(2)
11.8. New Technology with Disks	297	(3)
11.8.1. Disk Derivatization	297	(1)
11.8.2. Sample Preservation on Disk	298	(1)
11.8.3. Pipette-Tip Extraction Disk	299	(1)
Suggested Reading	300	(1)
References	301	(2)
CHAPTER 12 NEW TECHNOLOGY IN SOLID-PHASE EXTRACTION	303	(28)
12.1. Solid-Phase Microextraction	303	(6)
12.1.1. Design	303	(2)
12.1.2. Theory	305	(1)
12.1.3. Examples of Solid-Phase Microextraction	306	(3)
12.2. Matrix Solid-Phase Dispersion	309	(2)
12.3. New Solid Phases	311	(12)
12.3.1. Graphitized Carbon	311	(1)
12.3.2. Functionalized Styrene-Divinylbenzene	312	(3)
12.3.3. Restricted-Access Sorbents	315	(4)
12.3.4. Affinity Solid-Phase Extraction	319	(2)
12.3.5. Molecular Recognition and Molecular-Imprinting Solid-Phase Extraction	321	(1)
12.3.6. Layered Sorbents	322	(1)
12.4. Small-Volume Solid-Phase Extraction	323	(1)
12.5. Derivatization on Solid-Phase Extraction Sorbents	323	(1)
12.6. Semipermeable Membrane Device	324	(2)
12.7. Future of Solid-Phase Extraction	326	(1)
Suggested Reading	327	(1)
References	328	(3)
APPENDIX SOLID-PHASE EXTRACTION ON THE INTERNET AND PRODUCT GUIDE	331	(8)
A.1. Web Sites	331	(2)
A.2. Product Guide	333	(6)
INDEX	339