期刊
SPECTROCHIMICA ACTA PART B-ATOMIC SPECTROSCOPY
卷 63, 期 2, 页码 142-153出版社
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.sab.2007.11.012
关键词
limit of detection; detection limit; heteroscedastic; bias
类别
It has been shown that the MARLAP (Multi-Agency Radiological Laboratory Analytical Protocols) for estimating the Currie detection limit, which is based on 'critical values of the non-centrality parameter of the non-central t distribution', is intrinsically biased, even if no calibration curve or regression is used. This completed the refutation of the method, begun in Part 2. With the field cleared of obstructions, the true theory underlying Currie's limits of decision, detection and quantification, as they apply in a simple linear chemical measurement system (CMS) having heteroscedastic, Gaussian measurement noise and using weighted least squares (WLS) processing, was then derived. Extensive Monte Carlo simulations were performed, on 900 million independent calibration curves, for linear, hockey stick and quadratic noise precision models (NPMs). With errorless NPM parameters, all the simulation results were found to be in excellent agreement with the derived theoretical expressions. Even with as much as 30% noise on all of the relevant NPM parameters, the worst absolute errors in rates of false positives and false negatives, was only 0.3%. (C) 2007 Elsevier B.V. All rights reserved.
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