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7: Detection Limits
The International Union of Pure and Applied Chemistry (IUPAC) defines a method’s detection limit as the smallest
concentration or absolute amount of analyte that has a signal significantly larger than the signal from a suitable blank
[IUPAC Compendium of Chemical Technology, Electronic Version]. Although our interest is in the amount of analyte, in
this section we will define the detection limit in terms of the analyte’s signal. Knowing the signal you can calculate the
analyte’s concentration, CA, or the moles of analyte, nA, using the equations
SA = kA CA or SA = kA nA
Let’s translate the IUPAC definition of the detection limit into a mathematical form by letting Smb represent the average
signal for a method blank, and letting σ represent the method blank’s standard deviation. The null hypothesis is that the
mb
analyte is not present in the sample, and the alternative hypothesis is that the analyte is present in the sample. To detect the
analyte, its signal must exceed Smb by a suitable amount; thus,
(SA )DL = Smb ± zσmb (4.7.1)
If σmb is not known, we can replace it with smb; Equation 4.7.1 then becomes
You can make similar adjustments to other equations in this section. See, for example, Kirchner, C. J. “Estimation of
Detection Limits for Environme tal Analytical Procedures,” in Currie, L. A. (ed) Detection in Analytical Chemistry:
Importance, Theory, and Practice; American Chemical Society: Washington, D. C., 1988.
The value we choose for z depends on our tolerance for reporting the analyte’s concentration even if it is absent from the
sample (a type 1 error). Typically, z is set to three, which, from Appendix 3, corresponds to a probability, α , of 0.00135.
As shown in Figure 4.7.1 a, there is only a 0.135% probability of detecting the analyte in a sample that actually is analyte-
free.
Figure 4.7.1 : Normal distribution curves showing the probability of type 1 and type 2 errors for the IUPAC detection limit.
(a) The normal distribution curve for the method blank, with Smb = 0 and σ = 1. The minimum detectable signal for the
mb
analyte, (SA)DL, has a type 1 error of 0.135%. (b) The normal distribution curve for the analyte at its detection limit,
(SA)DL= 3, is superimposed on the normal distribution curve for the method blank. The standard deviation for the analyte’s
signal, σ , is 0.8, The area in green represents the probability of a type 2 error, which is 50%. The inset shows, in blue, the
A
As shown in Figure 4.7.2 , the limit of identification provides an equal probability of a type 1 and a type 2 error at the
detection limit. When the analyte’s concentration is at its limit of identification, there is only a 0.135% probability that its
signal is indistinguishable from that of the method blank.
Figure 4.7.2 : Normal distribution curves for a method blank and for a sample at the limit of identification: Smb = 0;
= 1; σ = 0.8 ; and (S )
σmb A A LOI = 0 + 3 × 1 + 3 × 0.8 = 5.4. The inset shows that the probability of a type 1 error
(0.135%) is the same as the probability of a type 2 error (0.135%).
The ability to detect the analyte with confidence is not the same as the ability to report with confidence its concentration,
or to distinguish between its concentration in two samples. For this reason the American Chemical Society’s Committee on
Environmental Analytical Chemistry recommends the limit of quantitation, (SA)LOQ [“Guidelines for Data Acquisition and
Data Quality Evaluation in Environmental Chemistry,” Anal. Chem. 1980, 52, 2242–2249 ].