A step-wise approach to the determination of the lower limit of analysis of the calibration line

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

A method is presented of stipulating the extension of the calibration line in analytical chemistry. The method is based on a combination of chemometric data interpretation and the calculation of the minimum standard deviation (STDEV) of experiments. From the depiction of the STDEV of a straight line versus the residuals, the more favorable concentration range of calibration could be obtained by iteration using only a few steps. This condition links the lower limit of analysis (LLA) to an upper limit of analysis (ULA), and, thus, completes the statistically appropriate extension of the calibration line. In addition, a minimum STDEV of measurement was expressed in terms of the STDEV on the slope (s a ) and on the intercept (s b ), and the calculation was performed by using a modified version of the law of propagation of errors (LPE). The method was validated on experiments of gas chromatography (GC), liquid chromatography (LC), electrochemistry, flow-injection analysis (FIA), atomic emission spectrometry (AES), flame atomic absorption spectrometry (FAAS), and inductively coupled-plasma mass spectrometry (ICP-MS). A novel definition of the ULA was proposed as the concentration where the response started to deviate significantly from linearity, also taking into account the level of uncertainty. The proposed method facilitates the determination of the concentration range of calibration and LLA in one working operation. In order to promote reliability, it was proposed that the number of repetitions of analysis should be high, preferably above 100, in order to fulfill the conditions of the central-limit theorem.

Original languageEnglish
Pages (from-to)308-319
Number of pages12
JournalJournal of Analytical Chemistry
Volume63
Issue number4
DOIs
Publication statusPublished - Apr 1 2008

Fingerprint

Calibration
Inductively coupled plasma mass spectrometry
Atomic absorption spectrometry
Liquid chromatography
Electrochemistry
Gas chromatography
Spectrometry
Experiments
Chemical analysis
Uncertainty

All Science Journal Classification (ASJC) codes

  • Analytical Chemistry

Cite this

@article{1cd06c8637114c12b116f4c299152caf,
title = "A step-wise approach to the determination of the lower limit of analysis of the calibration line",
abstract = "A method is presented of stipulating the extension of the calibration line in analytical chemistry. The method is based on a combination of chemometric data interpretation and the calculation of the minimum standard deviation (STDEV) of experiments. From the depiction of the STDEV of a straight line versus the residuals, the more favorable concentration range of calibration could be obtained by iteration using only a few steps. This condition links the lower limit of analysis (LLA) to an upper limit of analysis (ULA), and, thus, completes the statistically appropriate extension of the calibration line. In addition, a minimum STDEV of measurement was expressed in terms of the STDEV on the slope (s a ) and on the intercept (s b ), and the calculation was performed by using a modified version of the law of propagation of errors (LPE). The method was validated on experiments of gas chromatography (GC), liquid chromatography (LC), electrochemistry, flow-injection analysis (FIA), atomic emission spectrometry (AES), flame atomic absorption spectrometry (FAAS), and inductively coupled-plasma mass spectrometry (ICP-MS). A novel definition of the ULA was proposed as the concentration where the response started to deviate significantly from linearity, also taking into account the level of uncertainty. The proposed method facilitates the determination of the concentration range of calibration and LLA in one working operation. In order to promote reliability, it was proposed that the number of repetitions of analysis should be high, preferably above 100, in order to fulfill the conditions of the central-limit theorem.",
author = "Andersen, {J. E.T.}",
year = "2008",
month = "4",
day = "1",
doi = "10.1007/s10809-008-4002-z",
language = "English",
volume = "63",
pages = "308--319",
journal = "Journal of Analytical Chemistry",
issn = "1061-9348",
publisher = "Maik Nauka-Interperiodica Publishing",
number = "4",

}

A step-wise approach to the determination of the lower limit of analysis of the calibration line. / Andersen, J. E.T.

In: Journal of Analytical Chemistry, Vol. 63, No. 4, 01.04.2008, p. 308-319.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A step-wise approach to the determination of the lower limit of analysis of the calibration line

AU - Andersen, J. E.T.

PY - 2008/4/1

Y1 - 2008/4/1

N2 - A method is presented of stipulating the extension of the calibration line in analytical chemistry. The method is based on a combination of chemometric data interpretation and the calculation of the minimum standard deviation (STDEV) of experiments. From the depiction of the STDEV of a straight line versus the residuals, the more favorable concentration range of calibration could be obtained by iteration using only a few steps. This condition links the lower limit of analysis (LLA) to an upper limit of analysis (ULA), and, thus, completes the statistically appropriate extension of the calibration line. In addition, a minimum STDEV of measurement was expressed in terms of the STDEV on the slope (s a ) and on the intercept (s b ), and the calculation was performed by using a modified version of the law of propagation of errors (LPE). The method was validated on experiments of gas chromatography (GC), liquid chromatography (LC), electrochemistry, flow-injection analysis (FIA), atomic emission spectrometry (AES), flame atomic absorption spectrometry (FAAS), and inductively coupled-plasma mass spectrometry (ICP-MS). A novel definition of the ULA was proposed as the concentration where the response started to deviate significantly from linearity, also taking into account the level of uncertainty. The proposed method facilitates the determination of the concentration range of calibration and LLA in one working operation. In order to promote reliability, it was proposed that the number of repetitions of analysis should be high, preferably above 100, in order to fulfill the conditions of the central-limit theorem.

AB - A method is presented of stipulating the extension of the calibration line in analytical chemistry. The method is based on a combination of chemometric data interpretation and the calculation of the minimum standard deviation (STDEV) of experiments. From the depiction of the STDEV of a straight line versus the residuals, the more favorable concentration range of calibration could be obtained by iteration using only a few steps. This condition links the lower limit of analysis (LLA) to an upper limit of analysis (ULA), and, thus, completes the statistically appropriate extension of the calibration line. In addition, a minimum STDEV of measurement was expressed in terms of the STDEV on the slope (s a ) and on the intercept (s b ), and the calculation was performed by using a modified version of the law of propagation of errors (LPE). The method was validated on experiments of gas chromatography (GC), liquid chromatography (LC), electrochemistry, flow-injection analysis (FIA), atomic emission spectrometry (AES), flame atomic absorption spectrometry (FAAS), and inductively coupled-plasma mass spectrometry (ICP-MS). A novel definition of the ULA was proposed as the concentration where the response started to deviate significantly from linearity, also taking into account the level of uncertainty. The proposed method facilitates the determination of the concentration range of calibration and LLA in one working operation. In order to promote reliability, it was proposed that the number of repetitions of analysis should be high, preferably above 100, in order to fulfill the conditions of the central-limit theorem.

UR - http://www.scopus.com/inward/record.url?scp=42149120130&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=42149120130&partnerID=8YFLogxK

U2 - 10.1007/s10809-008-4002-z

DO - 10.1007/s10809-008-4002-z

M3 - Article

AN - SCOPUS:42149120130

VL - 63

SP - 308

EP - 319

JO - Journal of Analytical Chemistry

JF - Journal of Analytical Chemistry

SN - 1061-9348

IS - 4

ER -