SAP/CSC/CAM/AAS-031

Oct 2004

HOW TO DETERMINE LIMIT OF DETECTION IN

ATOMIC ABSORPTION SPECTROSCOPY

Introduction
According to IUPAC(1), limit of detection (LOD), expressed as the concentration, cL is
derived from the smallest measure, xL, that can be detected with reasonable certainty for a
given analytical procedure. The value for xL is given by the equation:
(1)

xL
xbl
sbl

=
=
=

xbl + ksbl

where
mean of blank measurements
standard deviation of the blank measurements

The values for xbl and sbl are found experimentally by making a sufficiently large number of
measurements, say 20. Also, a value of 3 for k in equation (1) is strongly recommended.
Hence, equation (1) becomes:
(2)
=
xL
xbl + 3sbl
In atomic absorption spectroscopy (AAS), a calibration curve is used to determine the
unknown concentration in a sample. The calibration curve can be represented by the
equation:
(3)
Absorbance
=
(Slope x concentration) + intercept
For determination of LOD:
Absorbance
Concentration
Intercept

=
=
=

Hence, from equations (2) and (3),

=
xL
=
xbl + 3sbl
=
3sbl
(4)
LOD
=

xL
cL = LOD
xbl
(Slope x cL ) + xbl
(Slope x LOD) + xbl
Slope x LOD

3sbl / Slope

The Slope in equation (4), which is also known as sensitivity, is determined using:
(5)
Slope
=
(x1 - xbl) / (c1 - cbl)
where
=
Mean absorbance of first standard solution
x1
=
Mean absorbance of blank solution
xbl
=
Concentration of first standard solution
c1
=
Concentration of blank solution = 0
cbl
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In equation (5), the slope is determined using a blank and standard solution. Preferably, the
concentration of the standard solution should be close to the concentration of LOD. As an
example, a rough estimate can be obtained from characteristic concentration (1% absorption)
the concentration of c1 is about 10 times higher than concentration of characteristic
concentration. Alternatively, the slope can also be determined by using a series of standard
solutions to generate the calibration curve - in most AAS instruments, the slope is calculated
by the software and displayed in the results.
By substituting equation (5) into equation (4), this becomes:
(6)
LOD
=
3sbl .c1 / (x1 - xbl)

Method
(a) Generate a calibration curve using a blank solution and a standard solution with

concentration about 10 times higher than concentration of characteristic concentration to

obtain c1, x1 and xbl .
(b) Analyse a blank solution about 20 times to obtain sbl .
(c) Substitute the values obtained in steps (a) and (b) in equation (6) to obtain LOD.
The calculations are shown below as an example.
Conc (ppm)
0.0
0.2
0.5
1.0

Abs
0.0036
0.0533
0.1222
0.2241

SD of blank solution measured 20

times = 0.0001295

Based on the table above, sbl = 0.0001295; c1 = 0.2 ppm; x1 = 0.0533; xbl = 0.0036
Hence, LOD = (3 x 0.001295 x 0.2) / (0.0533 0.0036)
= 0.016 ppm
Alternatively, the calculation using the slope value obtained by the AAS software is also
shown below.
Abs = 0.219383Conc + 0.00756212
From equation (4), LOD = 3sbl / Slope
= 3 x 0.001295 / 0.219383
= 0.018 ppm
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Shimadzu (Asia Pacific) Pte Ltd, Singapore

Reference
(1) www.iupac.org/publications/analytical_compendium/

~ The End ~

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Shimadzu (Asia Pacific) Pte Ltd, Singapore