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Published in:
Principles of Identification Read chapter Read first chapter

2011 | OriginalPaper | Chapter

4. Reliability and Errors of Identification

Author : Boris L. Milman

Published in: Chemical Identification and its Quality Assurance

Publisher: Springer Berlin Heidelberg

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Abstract

In this chapter, approaches to estimating reliability and errors of detection and identification are considered. Related terminology is presented; reliability of identification is defined as a probability of its true result. False results are demonstrated to be attributes of determination of low analyte amounts by screening methods. Formulas for calculating rates of true and false, positive and negative results are given. The rates are derived both from tests using analytical standards (blank samples) and upon verification of screening results by confirmatory methods/techniques. A replication of analytical determinations is also considered, including Bayesian statistics. Limit characteristics of detection and identification are treated.
It is noted that confirmatory methods based on spectrometry must be free of identification errors. Nevertheless, errors occur if methods are non-targeted, invalidated, or ad hoc. True and false results obtained with use of spectral techniques are discussed in terms of matching spectra. A best/good or poor matching resulting in a high or low match factor means a good/fair or poor chance respectively of accepting an identification hypothesis. Different match factors calculated in mass spectrometry and also NMR, IR-, and UV–V is spectroscopy are outlined, with many details with regard to searches in reference spectral libraries. Further, a probability interpretation of match factors is considered, which is essential for identification of peptides and proteins in proteomics. Other approaches to deriving a probability of identification from analytical/spectral data are also noted. This kind of probability, as well as the reported result of identification, can be expressed in words.

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previous chapter Probability, Statistics, and Related Methods
next chapter Target Identification in Methods
Footnotes
1
I.e., specificity is 100% selectivity.
 
2
This is
the minimum concentration or mass of the analyte that can be quantified with acceptable accuracy and precision [60]
The limit of quantification in such definition is close to the concept of minimum required performance limit (MRPL), i.e.,
… minimum content of an analyte in a sample, which at least has to be detected and confirmed [44].
Modern MRPL values, e.g., setting for pharmaceutical residues in animal products are very low at 0.3–1.0 μg/kg [61].
There is another synonymic term for low limit amount which can be measured. It is lowest calibrated level:
the lowest concentration (or mass) of analyte with which the determination system is successfully calibrated… [60]
 
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Metadata
Title
Reliability and Errors of Identification
Author
Boris L. Milman
Copyright Year
2011
Publisher
Springer Berlin Heidelberg
Book
Chemical Identification and its Quality Assurance

Print ISBN: 978-3-642-15360-0

Electronic ISBN: 978-3-642-15361-7

Copyright Year: 2011

DOI
https://doi.org/10.1007/978-3-642-15361-7_4

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