Summary
A method to determine the limit of detection (LOD) in high performance liquid chromatography (HPLC) is described. The power spectral density of instrumental baseline variation is fitted by the simplex least squares methods with a mixed random process of white noise and Markov process as a model. The white noise is characterized by standard deviation (SD),\(\tilde w\); the Markov process by the SD,\(\tilde m\), and auto-correlation degree, ρ. All required parameters for calculating the LOD signal are obtained by experiment without repeat measurements. No arbitrary constants are needed. The LOD signal is uniquely determined and is characterized by 33.3 % relative standard deviation (RSD) of analyte measurements and 0.13 % of the error of the first type. This signal also specifies that the signal-to-noise ratio =3, using the definition of noise originating from the white noise and Markov process. The theoretical conclusion is verified by the Monte Carlo simulation using real baseline and peaks. The LOD concentrations for naphthalene, acenaphthene, pyrene and perylene are given.
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Y. Hayashi, R. Matsuda, Anal. Chem.66, 2874 (1994).
P. W. J. M. Boumans, Anal. Chem.66, 459A (1994).
G. L. Long, J. D. Winefordner, Anal. Chem.55, 712A (1983).
L. H. Keith, W. Crummett, J. Deegan, Jr.,R. A. Libby, J. K. Taylor, G. Wentler, Anal. Chem.55, 2210 (1983).
D. Lambert, B. Peterson, I. Terpenning, Journal of the American Statistical Association86, 266 (1991).
Office of Health Studies. Chemicals in the environment, 1993.
L. A. Currie, Pure Appl. Chem.64, 455 (1992).
L. S. Ettre, Pure Appl. Chem.65, 819 (1993).
L. A. Currie, G. Svehla, Pure Appl. Chem.66, 595 (1994).
L. A. Currie, IUPAC project 18/83, Recommendation for nomenclature in evaluation of analytical methods, draft 1991,
R. Ferrús, M. R. Egea, Anal. Chim. Acta287, 119 (1994).
W. J. Taraszewski, D. T. Haworth, B. D. Pollard, Anal. Chim. Acta157, 73 (1984).
J. P. Foley, J. G. Dorsey, Chromatographia18, 503 (1984).
R. Kaiser, Chromatographia4, 123 (1971).
R. Kaiser, Chromatographia4, 215 (1971).
R. E. Synovec, E. S. Yeung, Anal. Chem.57, 2162 (1985).
H. C. Smit, H. L. Walg, Chromatographia8, 311 (1975).
C. N. Renn, R. E. Synovec, Anal. Chem.60, 1829 (1933).
J. F. K. Huber, J. A. R. J. Hulsman, C. A. M. Meijers, J. Chromatogr.62, 79 (1971).
E. H. Piepmeier, Anal. Chem.48, 1296 (1976).
Y. Hayashi, R. Matsuda, Chromatographia, accepted for publication.
M. Hino, Spectral Analysis (Supekutoru Kaiseki), 8th ed.; Tokyo: Asakura Shoten, 1982.
Y. Hayashi, R. Matsuda, Anal. Sci.10, 553 (1994).
H. Barth, E. Dallmeier, G. Courtois, H. E. Keller, B. L. Karger, J. Chromatogr.83, 289 (1973).
A. W. Westerberg, Anal. Chem.41, 1770 (1969).
L. R. Snyder, Chrom. Sci.10, 200 (1972).
J. P. Foley, J. Chromatogr.384, 301 (1987).
A. N. Papas, M. F. Delaney, Anal. Chem.59, 54A (1987).
N. Dyson, Chromatographic integration methods, Cambridge: Royal Society of Chemistry, 1990.
E. Grushka, I. Zamir, Chemical Analysis, 1989, Chapter 13.
S. R. Bakalyar, R. A. Henry, J. Chromatogr.126, 327 (1976).
R. P. W. Scott, C. E. Reese, J. Chromatogr.138, 283 (1977).
I. Halász, P. Vogtel, J. Chromatogr.142, 241 (1977).
L. R. Snyder, S. van der Wal, Anal. Chem.53, 877 (1981).
Y. Hayashi, R. Matsuda, Chemom. Intell. Lab Syst.18, 1 (1993).
Y. Hayashi, R. Matsuda, Advances in Chromatography, 1994, Chapter 7.
H. Kaiser, Spectrochim. Acta3, 40 (1947).
C. Th. J. Alkemade, W. Snelleman, G. D. Boutilier, B. D. Pollard, J. D. Winefordner, T. L. Chester, N. Omenetto, Spectrochim. Acta, Part B,33, 383 (1978).
G. D. Boutilier, B. D. Pollard, J. D. Winefordner, T. L. Chester, N. Omenetto, Spectrochim. Acta, Part B,33, 401 (1978).
C. Th. Alkemade, W. Snelleman, G. D. Boutilier, J. D. Winefordner, Spectrochim. Acta, Part B,35, 261 (1980).
J. D. Winefordner, R. Avni, T. L. Chester, J. J. Fizgerald, L. P. Hart, D. J. Johnson, F. W. Plankey, Spectrochim. Acta, Part B,31, 1 (1976).
A. Bezegh, J. Janata, Anal. Chem.59, 494A (1987).
T. Hirschfeld, Appl. Spectrosc.30, 67 (1976).
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Hayashi, Y., Matsuda, R. & Poe, R.B. Prediction of precision from signal and noise measurement in liquid chromatography: Limit of detection. Chromatographia 41, 66–74 (1995). https://doi.org/10.1007/BF02688002
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DOI: https://doi.org/10.1007/BF02688002