4.6 Article

Limits of detection and decision. Part 2

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PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.sab.2007.11.018

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limit of detection; detection limit; noncentral t distribution; bias

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Extensive Monte Carlo studies of instrumental limits of detection (LODs) were performed on a simple univariate chemical measurement system having homoscedastic, Gaussian measurement noise and using ordinary least squares (OLS) processing of tens of millions of independent calibration curve data sets. It was found that experimental decision and detection limits in the content domain were distributed as scaled reciprocals of noncentral t variates. In the response domain, the decision and detection limits were distributed as scaled X variates. Rates of false negatives were found to be as expected statistically and no bias was found. However, use of detection limit expressions based on critical values of the noncentrality parameter of the noncentral t distribution were found to be significantly biased, resulting in substantial bias in rates of false negatives. (C) 2007 Elsevier B.V. All rights reserved.

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