7.10: Additional Resources

The following set of experiments and class exercises introduce students to the importance of sampling on the quality of analytical results.

• Bauer, C. F. “Sampling Error Lecture Demonstration,” J. Chem. Educ. 1985, 62, 253.
• Canaes, L. S.; Brancalion, M. L.; Rossi, A. V.; Rath, S. “Using Candy Samples to Learn About Sampling Techniques and Statistical Evaluation of Data,” J. Chem. Educ. 2008, 85, 1083–1088.
• Clement, R. E. “Environmental Sampling for Trace Analysis,” Anal. Chem. 1992, 64, 1076A–1081A.
• Dunn, J. G.; Phillips, D. N.; van Bronswijk, W. “An Exercise to Illustrate the Importance of Sample Preparation in Chemical Analysis,” J. Chem. Educ. 1997, 74, 1188–1191.
• Fillman, K. L.; Palkendo, J. A. “Collection, Extraction, and Analysis of Lead in Atmospheric Particles,” J. Chem. Edu. 2014, 91, 590–592.
• Fritz, M. D. “A Demonstration of Sample Segregation,” J. Chem. Educ. 2005, 82, 255–256.
• Guy, R. D.; Ramaley, L.; Wentzell, P. D. “An Experiment in the Sampling of Solids for Chemical Analysis”, J. Chem. Educ. 1998, 75, 1028–1033.
• Hartman, J. R. “An In-Class Experiment to Illustrate the Importance of Sampling Techniques and Statistical Analysis of Data to Quantitative Analysis Students,” J. Chem. Educ. 2000, 77, 1017–1018.
• Harvey, D. T. “Two Experiments Illustrating the Importance of Sampling in a Quantitative Chemical Analysis,” J. Chem. Educ. 2002, 79, 360–363.
• Herrington, B. L. “A Demonstration of the Necessity for Care in Sampling,” J. Chem. Educ. 1937, 14, 544.
• Kratochvil, B.; Reid, R. S.; Harris, W. E. “Sampling Error in a Particulate Mixture”, J. Chem. Educ. 1980, 57, 518–520.
• Ross, M. R. “A Classroom Exercise in Sampling Technique,” J. Chem. Educ. 2000, 77, 1015–1016.
• Settle, F. A.; Pleva, M. “The Weakest Link Exercise,” Anal. Chem. 1999, 71, 538A–540A.
• Vitt, J. E.; Engstrom, R. C. “Effect of Sample Size on Sampling Error,” J. Chem. Educ. 1999, 76, 99–100.

The following experiments describe homemade sampling devices for collecting samples in the field.

• Delumyea, R. D.; McCleary, D. L. “A Device to Collect Sediment Cores,” J. Chem. Educ. 1993, 70, 172–173.
• Rockwell, D. M.; Hansen, T. “Sampling and Analyzing Air Pollution,” J. Chem. Educ. 1994, 71, 318–322.
• Saxena, S., Upadhyay, R.; Upadhyay, P. “A Simple and Low-Cost Air Sampler,” J. Chem. Educ. 1996, 73, 787–788.
• Shooter, D. “Nitrogen Dioxide and Its Determination in the Atmosphere,” J. Chem. Educ. 1993, 70, A133–A140.

The following experiments introduce students to methods for extracting analytes from their matrix.

• “Extract-CleanTM SPE Sample Preparation Guide Volume 1”, Bulletin No. 83, Alltech Associates, Inc. Deerfield, IL.
• Freeman, R. G.; McCurdy, D. L. “Using Microwave Sample Decomposition in Undergraduate Analytical Chemistry,” J. Chem. Educ. 1998, 75, 1033–1032.
• Snow, N. H.; Dunn, M.; Patel, S. “Determination of Crude Fat in Food Products by Supercritical Fluid Extraction and Gravimetric Analysis,” J. Chem. Educ. 1997, 74, 1108–1111.
• Yang, M. J.; Orton, M. L.; Pawliszyn, J. “Quantitative Determination of Caffeine in Beverages Using a Combined SPME-GC/MS Method,” J. Chem. Educ. 1997, 74, 1130–1132.

The following papers provides a general introduction to the terminology used in describing sampling.

• “Terminology—The key to understanding analytical science. Part 2: Sampling and sample preparation,” AMCTB 19, 2005.
• Majors, R. E. “Nomenclature for Sampling in Analytical Chemistry” LC•GC 1992, 10, 500–506.

Further information on the statistics of sampling is covered in the following papers and textbooks.

• Analytical Methods Committee “What is uncertainty from sampling, and why is it important?” AMCTB 16A, 2004.
• Analytical Methods Committee “Analytical and sampling strategy, fitness for purpose, and computer games,” AMCTB 20, 2005.
• Analytical Methods Committee “Measurement uncertainty arising from sampling: the new Eurachem Guide,” AMCTB No. 31, 2008.
• Analytical Methods Committee “The importance, for regulation, of uncertainty from sampling,” AMCTB 42, 2009.
• Analytical Methods Committee “Estimating sampling uncertainty—how many duplicate samples are needed?” AMCTB 58, 2014.
• Analytical Methods Committee “Random samples,” AMCTB 60, 2014.
• Analytical Methods Committee “Sampling theory and sampling uncertainty,” AMCTB 71, 2015.
• Sampling for Analytical Purpose, Gy, P. ed., Wiley: NY, 1998.
• Baiulescu, G. E.; Dumitrescu, P.; Zuaravescu, P. G. Sampling, Ellis Horwood: NY, 1991.
• Cohen, R. D. “How the Size of a Random Sample Affects How Accurately It Represents a Population,” J. Chem. Educ. 1992, 74, 1130–1132.
• Efstathiou, C. E. “On the sampling variance of ultra-dilute solutions,” Talanta 2000, 52, 711–715.
• Esbensen, K. H.; Wagner, C. “Theory of sampling (TOS) versus measurement uncertainty (MU)–A call for integration,” TRAC-Trend. Anal. Chem. 2014, 57, 93–106.
• Gerlach, R. W.; Dobb, D. E.; Raab, G. A.; Nocerino, J. M. J. Chemom. 2002, 16, 321–328.
• Gy, P. M. Sampling of Particulate Materials: Theory and Practice; Elsevier: Amsterdam, 1979.
• Gy, P. M. Sampling of Heterogeneous and Dynamic Materials: Theories of Heterogeneity, Sampling and Homogenizing; Elsevier: Amsterdam, 1992.
• Harrington, B.; Nickerson, B.; Guo, M. X.; Barber, M.; Giamalva, D.; Lee, C.; Scrivens, G. “Sample Preparation Composite and Replicate Strategy for Assay of Solid Oral Drug Products,” Anal. Chem. 2014, 86, 11930–11936.
• Kratochvil, B.; Taylor, J. K. “Sampling for Chemical Analysis,” Anal. Chem. 1981, 53, 924A–938A.
• Kratochvil, B.; Goewie, C. E.; Taylor, J. K. “Sampling Theory for Environmental Analysis,” Trends Anal. Chem. 1986, 5, 253–256.
• Meyer, V. R. LC•GC 2002, 20, 106–112.
• Rohlf, F. J.; AkÇakaya, H. R.; Ferraro, S. P. “Optimizing Composite Sampling Protocols,” Environ. Sci. Technol. 1996, 30, 2899–2905.
• Smith, R.; James, G. V. The Sampling of Bulk Materials; Royal Society of Chemistry: London, 1981.

The process of collecting a sample presents a variety of difficulties, particularly with respect to the analyte’s integrity. The following papers provide representative examples of sampling problems.

• Barceló, D.; Hennion, M. C. “Sampling of Polar Pesticides from Water Matrices,” Anal. Chim. Acta 1997, 338, 3–18.
• Batley, G. E.; Gardner, D. “Sampling and Storage of Natural Waters for Trace Metal Analysis,” Wat. Res. 1977, 11, 745–756.
• Benoit, G.; Hunter, K. S.; Rozan, T. F. “Sources of Trace Metal Contamination Artifacts during Collection, Handling, and Analysis of Freshwaters,” Anal. Chem. 1997, 69, 1006–1011
• Brittain, H. G. “Particle-Size Distribution II: The Problem of Sampling Powdered Solids,” Pharm. Technol. July 2002, 67–73.
• Ramsey, M. H. “Measurement Uncertainty Arising from Sampling: Implications for the Objectives of Geoanalysis,” Analyst, 1997, 122, 1255–1260.
• Seiler, T-B; Schulze, T.; Hollert, H. “The risk of altering soil and sediment samples upon extract prepa- ration for analytical and bio-analytical investigations—a review,” Anal. Bioanal. Chem. 2008, 390, 1975–1985.

The following texts and articles provide additional information on methods for separating analytes and inter- ferents.

• “Guide to Solid Phase Extraction,” Bulletin 910, Sigma-Aldrich, 1998.
• “Solid Phase Microextraction: Theory and Optimization of Conditions,” Bulletin 923, Sigma-Aldrich, 1998.
• Microwave-Enhanced Chemistry: Fundamentals, Sample Preparation, and Applications, Kingston, H. M.; Haswell, S. J., eds.; American Chemical Society: Washington, D.C., 1997.
• Anderson, R. Sample Pretreatment and Separation, Wiley: Chichester, 1987.
• Bettiol, C.; Stievano, L.; Bertelle, M.; Delfino, F.; Argese, E. “Evaluation of microwave-assisted acid extraction procedures for the determination of metal content and potential bioavailability in sediments,” Appl. Geochem. 2008, 23, 1140–1151.
• Compton, T. R. Direct Preconcentration Techniques, Oxford Science Publications: Oxford, 1993.
• Compton, T. R. Complex-Formation Preconcentration Techniques, Oxford Science Publications: Oxford, 1993.
• Hinshaw, J. V. “Solid-Phase Microextraction,” LC•GC Europe 2003, December, 2–5.
• Karger, B. L.; Snyder, L. R.; Harvath, C. An Introduction to Separation Science, Wiley-Interscience: N. Y.; 1973.
• Majors, R. E.; Raynie, D. E. “Sample Preparation and Solid-Phase Extraction”, LC•GC 1997, 15, 1106–1117.
• Luque de Castro, M. D.; Priego-Capote, F.; Sánchez-Ávila, N. “Is dialysis alive as a membrane-based separation technique?” Trends Anal. Chem. 2008, 27, 315–326.
• Mary, P.; Studer, V.; Tabeling, P. “Microfluidic Droplet-Based Liquid–Liquid Extraction,” Anal. Chem. 2008, 80, 2680–2687.
• Miller, J. M. Separation Methods in Chemical Analysis, Wiley-Interscience: N. Y.; 1975.
• Morrison, G. H.; Freiser, H. Solvent Extraction in Analytical Chemistry, John Wiley and Sons: N. Y.; 1957.
• Pawliszyn, J. Solid-Phase Microextraction: Theory and Practice, Wiley: NY, 1997.
• Pawliszyn, J. “Sample Preparation: Quo Vadis?” Anal. Chem. 2003, 75, 2543–2558.
• Sulcek, Z.; Povondra, P. Methods of Decomposition in Inorganic Analysis; CRC Press: Boca Raton, FL, 1989.
• Theis, A. L.; Waldack, A. J.; Hansen, S. M.; Jeannot, M. A. “Headspace Solvent Microextraction,” Anal. Chem. 2001, 73, 5651–5654.
• Thurman, E. M.; Mills, M. S. Solid-Phase Extraction: Principles and Practice, Wiley: NY, 1998.
• Zhang, Z.; Yang, M.; Pawliszyn, J. “Solid-Phase Microextraction,” Anal. Chem. 1994, 66, 844A–853A.