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LD Iupac. Article
LD Iupac. Article
The ability to quantify a trace ele- approaches (1-13). In spite of the fact examine the statistical meaning of
ment or molecule in chemical and bio- that the International Union of Pure limit of detection values in a format
logical matrices using specific analyti- and Applied Chemistry (IUPAC) consistent with the IUPAC definition.
cal methods is often viewed in terms adopted a model for the limit of detec- It is not intended to be a comprehen-
of the limit of detection. This limit of tion calculations in 1975 (I),and the sive review of the various methods of
detection is a number, expressed in ACS Subcommittee on Environmental calculating limit of detection values.
units of concentration (or amount), Analytical Chemistry reaffirmed this For a more complete review, the read-
that describes the lowest concentra. standard in 1980 (2),acceptance of er is referred to the excellent articles
tion level (or amount) of the element this model by the general analytical by Kaiser ( 3 4 , Boumans (7-9). Cur-
that an analyst can determine to be community has been slow. The result rie(lO),Glaseret al. IiI),aswellas
statistically different from an analyti- of this slow acceptance bas led to a available textbooks (12,13J. Rather,
cal blank (I).Although this definition great deal of uncertainty when limits this HEPOHT is intended to be a sim-
seems rather straightforward. signifi- of detection are used a s ~ abasis for ple and general discussion on methods
cant problems have been encountered comparison between various analytical for calculating limits of detection; it is
in expressing these values because of procedures, methods. or analytical in- geared to the analyst who does not
the various approaches to the term strumenffi. Unless the limits of detec- have a rigorous knowledge of statis-
“statistically different.” The calculat- tion are calculated in a consistent tics. In this examination, the signifi.
ed limit of detection for an element manner, the comparison may be cance of the limit of detection values
can easily vary an order of magnitude meaningless. will be emphasized, and the possible
through the use of different statistical It is the purpose of this REPORT to problems encnuntered when using
limit of detection values obtained tected with reasonable certainty for a generally plots of signal, x, vs. analyte
from non-IUPAC methods as a basis given analytical procedure” (I). This concentration, c, and are represented
for comparing methods and instru- concept is further clarified by the ACS as in Figure 1. The relationship be-
menta will be discussed. Also, two definition, which states “the limit of tween x and c can be obtained by per-
methods will be introduced that per- detection is the lowest concentration forming a linear regression analysis on
mit measurement errors in the analyt- of an analyte that an analytical pro- the data. This analytical calibration
ical sensitivity to be included in the cess can reliably detect” (2).To un- relationship cnn be expressed as
limit of detection calculation. These derstand what a reasonably certain
two methods as well as the IUPAC measure or a reliable detection is, the x=mc+i
method will be evaluated for their method of measurement as well as the
ability to incorporate these errors into errors (including noises) agsociated where m is the slope or analytical sen-
the numerical limit of detection. with the measurement must be well sitivity and i is the intercept. When an
understood. unknown sample containing the ana-
lyte is subjected to the analytical pro-
Definition cedure, a value, xu, can be measured.
The IUPAC definition, adopted in Measurements This value may then be inserted into
1975, states that “the limit of detec- Generally, most analytical methods Equation 1to determine the concen-
tion, expressed as a concentration CL require the construction of analytical tration of the unknown, cu. However,
(or amount, qL), is derived from the calibration curves for the determina- the ability to solve accurately for h~is
smallest measure, XL,that can be de- tion of unknowns. These cuwes are dependent upon how well the m and i
(3
+ - sm2
Taking the designated derivatives and
(19)
+ (- %)2sm2]1/2 (20)
and finally combining like terms
yields
s, =
[...+ si2 +(q2smj1/2
(21)
m