DETECTION : INTERNATIONAL UPDATE, AND SOME EMERGING DI-LEMMAS INVOLVING CALIBRATION, THE BLANK, AND MULTIPLE DETECTION DECISIONS

Abstract Detection and quantification capabilities represent fundamental performance characteristics of measurement processes, yet there have been decades of confusion and miscommunication regarding the underlying concepts and terminology. New, coordinated documents prepared by the International organization for standardization (ISO) [1] and the International union of pure and applied chemistry (IUPAC) [2] promise to alleviate this situation by providing, for the first time, a harmonized position of standards and recommendations for adoption by the international scientific community. The first section of this paper contains a brief introduction to the events leading to the ISO and IUPAC efforts. Section 2 consists of (1) a brief review of the history of `detection limits' in chemistry, illustrating the critical need for the development of a sound and uniform system of terms and symbols; and (2) a review of the ISO-IUPAC deliberations and the ensuing harmonized position on concepts and nomenclature. Section 3 treats fundamental applications of the underlying concepts, together with a series of unresolved or `open' questions involving: detection and quantification capabilities in the signal and concentration domains, respectively; and the link between calibration and detection and quantification limits, together with the blank-intercept dichotomy. Also included are special treatments and approximations, developed in part for the IUPAC document, involving the non-central-t, and the exact (non-normal) distribution of the estimated concentration. The final section ( Section 4 ) introduces issues and approaches to multiple independent and multivariate detection decisions and limits, and concludes with a glimpse at some challenges involving the multivariate blank and non-monotonic calibration functions.

[1]  H. Kaiser,et al.  Zum Problem der Nachweisgrenze , 1965 .

[2]  L. A. Currie,et al.  Nomenclature in evaluation of analytical methods including detection and quantification capabilities (IUPAC Recommendations 1995) , 1995 .

[3]  Diane Lambert,et al.  Nondetects, Detection Limits, and the Probability of Detection , 1991 .

[4]  Andre. Hubaux,et al.  Decision and detection limits for calibration curves , 1970 .

[5]  Anita Singh,et al.  Multivariate decision and detection limits , 1993 .

[6]  F. X. Rius,et al.  MULTIVARIATE DETECTION LIMITS ESTIMATORS , 1996 .

[7]  R. Royall.  Model robust confidence intervals using maximum likelihood estimators , 1986 .

[8]  G. Enderlein,et al.  Brownlee, K. A.: Statistical Theory and Methodology in Science and Engineering. Wiley, New York 1960; 570 S., $ 16,75 , 1961 .

[9]  Lloyd A. Currie,et al.  Detection in Analytical Chemistry: Importance, Theory, and Practice , 1987 .

[10]  C. Andrew. Clayton,et al.  Detection limits with specified assurance probabilities , 1987 .

[11]  M. L. Tiku,et al.  A NOTE ON THE DISTRIBUTION OF THE DOUBLY NON‐CENTRAL F DISTRIBUTION1 , 1972 .

[12]  E. S. Pearson,et al.  Charts of the power function for analysis of variance tests, derived from the non-central F-distribution. , 1951, Biometrika.

[13]  L. A. Currie,et al.  LIMITS FOR QUALITATIVE DETECTION AND QUANTITATIVE DETERMINATION. APPLICATION TO RADIOCHEMISTRY. , 1968 .

[14]  J. Edward Jackson,et al.  Quality Control Methods for Several Related Variables , 1959 .

[15]  F. Massey,et al.  Introduction to Statistical Analysis , 1970 .

[16]  L. A. Currie,et al.  Lower limit of detection: definition and elaboration of a proposed position for radiological effluent and environmental measurements , 1984 .

[17]  L. A. Currie.  In pursuit of accuracy: Nomenclature, assumptions, and standards , 1992 .

[18]  Multivariate detection limits for selected ion monitoring gas chromatography — mass spectrometry , 1988 .

[19]  H. Scheffé.  A Statistical Theory of Calibration , 1973 .

[20]  Dulal K. Bhaumik,et al.  Statistical Methods for Groundwater Monitoring , 1994 .

[21]  Rupert G. Miller.  Simultaneous Statistical Inference , 1966 .

[22]  E. T. Hall,et al.  Radiocarbon dating of the Shroud of Turin , 1989, Nature.

[23]  Anders Hald,et al.  Statistical Theory with Engineering Applications , 1952 .

[24]  H. Kaiser.  Zur Definition der Nachweisgrenze, der Garantiegrenze und der dabei benutzten Begriffe , 1966 .

[25]  Candin Liteanu,et al.  Statistical theory and methodology of trace analysis , 1980 .

[26]  L. A. Currie,et al.  Fossil- and bio-mass combustion: C-14 for source identification, chemical tracer development, and model validation☆ , 1994 .

[27]  L. Currie.  The Measurement of Environmental Levels of Rare Gas Nuclides and the Treatment of Very Low-Level Counting Data , 1972 .

[28]  Lloyd A. Currie,et al.  Nomenclature for the presentation of results of chemical analysis (IUPAC Recommendations 1994) , 1994 .

[29]  Lawrence H. Keith,et al.  Principles of environmental analysis , 1983 .