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I

Figure 1. Analytical calibration CUNB


of signal, x, vs. concentration, c
The unknown Signal. xu, is re@& 10 an w h o m
con(amat1m. cu, tJwcu$ the equation x = mc +
i. where rn io the slop and I is Uw lnteroept ot
me line

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

7 1 2 ~ ANALYTICAL CHEMISTRY, VOL.55. NO. 7, JUNE 1 9 8 ~ 000%2700/83/035 1-7 12ASO 1.50/0


Q 1983American Chemical Society
Gary L. Long
J. D. Winefordner
Department of Chemism
University of Flwida
Galmville. FIB. 32611

Flgure 2. Normal distribution curve for


a measured x variable
me pink shaded wet. 01. represents me pobabll-
hvmt XE 3 A,( + k(r)OrxL a(& + 3%)

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

ANALYTiCAL CHEMISTRY. VOL. 55. NO. 7, JUNE 1983 713,.


values are known. As long as the cali- as shown in Figure 3. The limit of de-
bration curve is obtained in the linear tection is found by relating ksB to a
response region of the method, the concentration value by dividing by the
more points obtained in the construc- slope of the calibration curve line ob-
tion of the calibration curve the better tained from the linear regression anal-
defined them value will be. Also, if ysis. However, the value obtained
points are sampled near the origin, the can only be a true reflection of the
i value may be better defined. How- limit of detection when m is well-de-
ever, if the m and i values are not well- fined and i is essentially 0.
defined because of nonlinearity in the The use of k = 3 allows a confidence
calibration curve or a poor choice of level of 99.86% that XL Z (FB 3se)+
calibration curve ranges, the result of for a measurement based on the error
the unknown determination, eu,may of the blank signal following a normal
he subject to considerable error.
I
--
I
-
distribution. I t must he emphasized
that if XB does not follow a normal
distribution, then the probability
Statistics Figure 3. Analytical calibration curve +
that XL 2 (XB 3.38)would he
The amount of error associated with of signal, x, vs. concentration, c, show- lOO(1 - l k z ) ,or 89%according to
a measurement of x can be statistical- ing the relationship of ks. to the limit of Tschebyscheffs inequality ( 5 ) .Hence,
ly estimated. Most measurements are detection, q values of k < 3 should not be used for
subject to error that follows a normal limit of detection calculations.
distribution. If a sufficiently large
number of observations is made, plot- Other Approaches
ting the measured responses would The majority of the other approach-
nB
produce a curve similar to that shown es to calculating CL values are similar
in Figure 2. The mean value of the re- (XBj - XBB)'
j-1 to the IUPAC model in that SB and k
sponses, p, occurs a t the center of the Sgz = (4) factors are involved. However, it is be-
curve. The curve is symmetric around (ne - 1)
cause of these terms that trouble may
p and extends outward in units of for nB Observations. Because a finite he encountered when CL values are
standard deviation, u. Since this curve small number of blank readings is nor- used as a basis for the comparison be-
includes all x values that could be ob- mally taken, e.g., nB = 20 or greater, tween procedures, methods, or instru-
tained from the procedure for the SB must be used instead of OB. If a ments. The most widely debated of
sample, the area under the curve can sample of this size is used, SB can be the two factors has been the choice of
be expressed in terms of probability, P considered to he a reasonable indica- a value fork. Kaiser was perhaps the
(i.e., there is a 100% chance, P = 1, tor of OB. If the random error follows a first to stress the use of k = 3 for cL
that a measured x value would fall normal distribution, a plot of these re- values ( 3 , 4 ) .This value has also been
somewhere under the curve). sponses (frequency of occurrence vs. agreed upon by other authors (9,13),
The relationship between area and XB values) would resemble Figure 2. by IUPAC ( I , 14),and by the ACS (2).
probability can he measured to esti- The probability that the smallest dis- A value of 2 for k had been initially
mate the chance that a newly mea- cernible analytical signal, XL. can be suggested ( 8 )hut this value corre-
sured x value, XE, would he a certain measured and not be a random fluctu- sponds to a 97.7% confidence level for
number of standard deviation units ation of the blank is dependent upon normal distribution and 75% for a
.away from the mean response, p. In how many standard deviation units XL nonnormal distribution of measure- -.
Figure 2, XE is shown to the right of p is from XB. If XL is 3SB away from XB, ment error.
and can be measured to be ku away the area to the right of XL is no less Although the use of k = 3 instead of
from p. By dissecting the curve with a than 0.0013.Thus, there is a 0.13% k = 2 s l i g k y increases the CL value, it
line drawn a t this x value, the area to chance that a signal measured a t XL or is clear that e~ values must differ by a
the right of the line, a,is the prohabil- greater would be the result of a ran- factor of three for the values to be sig-
+
ity that XE 3 ( p ku). This chance, dom fluctuation of the blank signal. nificantly different. Nevertheless, fac-
which is represented by the pink shad- This small chance of error can then tors of less than three have been com-
ed area, can be determined from fulfill the reouirement of a reasonablv monly used for comparison purposes.
certain signal. In order to minimize confusion,
In defining CL, IUPAC states that IUPAC suggested that XL values be re-
XL = XB + kSB (5)
ported in all literature with their k
value, x ~ ( k - 8 ) . I t would be extremely
where the XE value is ku away from p,
(Le., (XE - p ) / u = k). where k is a numerical factor chosen in useful to go one step further and in-
This illustration can also be used to accordance with the confidence level clude the k values when CL values are
aid in the explanation of the smallest desired. The CL is a function of XL and reported, C L ( ~ = S ) .This change would
detectable signal, XL, in the IUPAC therefore be beneficial because CL values are
definition. When the determination of more commonly reported than XL
a limit of detection is performed, values.
blank measurements, XB, are normally A problem encountered in the com-
taken. The question, however, is "how where m is the analytical sensitivity. parative use of CL values is the use of
well are these XB values known?" A Because the mean blank reading, XB, the standard deviation of the mean, sg
mean value of the blank responses, XB, is not always 0, the signal must be ( 1 1 ) . the pooled standard deviation, sp
can he calculated as background corrected. By substituting (7,12), or the relative standard devia-
Equation 5 into Equation 6, Equation tion (RSD)( 7 , 9 ) .Although each of
ng
7 is obtained these standard deviation expressions
XBi
is important and has its place in ana-
(3) lytical chemistry, the use or misuse of
these expressions in CL calculations
and the standard deviation as This definition of e~ can be illustrated may result in significant deviation

714A ANALYTICAL CHEMISTRY, VOL. 55. NO. 7, JUNE 1983


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In many ICP determinations, the
RSD has been measured to be 0.01 (as
determined by emission flicker noise).
Unfortunately, many ICP m values in
papers and current manufacturers’
bulletins have been calculated with
k = 2. Inserting these values into
Equation 13 yields

A problem that may be encountered


Figure 4. Normal distribution C U N ~ Sfor the blank observation. %(pink line), the with thii approach is that the RSD for
llmit of detection. x (blue line), and the limit of identification, xI (purple line) some spectrometric detection systems
M e all standard deviations follow a m I dlswibutim and are equal may be >0.01.Before using this meth-
od, an analyst should reconfirm the
validity of RSD 4 0.01. Failure to
from the IUPAC model. measure and correct for high RSD val-
The standard deviation of the mean ues could result in erroneous val-
(or the standard error), sg, is ex- ues. An attempt to compare an ICP q,
pressed by This relationship is useful in ex- value obtained from this method and
pressing the “concentrational limit of an IUPAC value for the same anal-
determination,” CD (7). Here, the mea- ysis procedure would be meaningless.
sure XD corresponding to CD is defined A well-based but seldom used con-
as cept in the calculation of detection
This value is calculated by dividing
limits is the limit of identification, 9.
the standard deviation of the blank XD = ko SB (12) as described by Boumans (7) or the
measures, 8 8 , by the square root of the limit of guarantee for purity, cc, de-
number of blank Observations, nB. where SB is the standard deviation of
the blank (not the RSD), and kD is a scribed by Kaiser (3).These concepts
Usually when ss values are used, the k are essentially the same and are based
factor is replaced by a t distribution confidence factor that is defined by
the reciprocal of the magnitude of the on the idea that the lowest statistical-
value. Even though the t values reflect ly discernible signal should be
the problem of defining a standard de- RSD value. For a maximum allowed
RSD of5%, kD = 20 and for a RSD of
viation for a finite number of ohserva-
tions, 3SB > t. SB/(nB)’/2 for a = 0.005 lG%, kD = 10. XI = XL + 381
and five observations (four degrees of Another limiting expression involv- where 81 is the error associated with the
freedom). This inequality greatly in- ing RSD values involves the rearrang- measurements at the XI level, or
creases as ne increases. If a large num- ing of Equation 7 (9). If the back-
ber of observations are taken on the ground signal is included in the nu-
blank, say 30, the use of the t and merator and denominator of Equation
will reduce the value of CL by a factor
7, then if 81 = SB. This concept is illustrated in
of six from the IUPAC model.
The use of the pooled standard de.
viation includes the number of blank
measurements as well as sample mea-
surements. Generally, the pooled stan Table 1. Statlstlcal Expresslons for the Slope and Intercept
dard deviation, SP, is expressed as

where 8s is the standard deviation ofa


sample measurement and ng is the
number of sample obnervations. If e
= SB, then Equation 9 reduces to

For ns = 1, sp is essentially the same


n
as SB. However, if ns and n e are both
large, sp < SB. Again, the use of a largt
number of observations as mentioned
above would cause a sirmifieant reduc-
tion in the value as eompared to the
IUPAC model.
Another common practice involves
the use of the RSD, which is d e f i e d
as

716A ANALYTICAL CHEMISTRY, VOC. 55. NO. 7, JUNE 1983


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Figure 4. When measurements are
made for a sample, the x values ob-
tained should follow normal distribu-
tion around a mean value. If a sample
were measured to have a mean a t the
XL value, the distribution of these x
values around XL would resemble the
blue line in Figure 4.One-half of the
time the measurement would fall
below the XL value and could not be
considered a true signal according to
the IUPAC definition. To avoid this
high probability, the limit of XI is set
at 3sr away from XL. This level is cbo-
sen so the areas a and 0 are equal. If
SI = SB then this level is 3SB away from
XL or 6 s away
~ from ZB. By using Figure 5. Analytical calibration curve
k = 3, the area of the XI distribution of signal, x. vs. concentration, c, show-
curve below XL, (3, is no less than ing graphical approach to limit of detec-
0.0013. Thus, there is a 0.13% chance tion calculation
that an x value measured a t XI would While dashed lines are Uw limit of emor bars. cL
is obtalned ham xc if no m w occurs in slope. ca
fall below the XL limit and not be con- is obtained tmm xc if slope error is significant
sidered as a true signal.
This idea of further statistically
separating the blank measurements dard deviation of the slope, s, in the
distributions and true signal distribu- CL expression. The second method, a
tions has been proposed by the ACS propagation of errors approach, con-
Subcommittee on Environmental An- siders the standard deviation of the
alytical Chemistry and has been concentration, sE. This value is calcu-
termed the limit of quantitation (2). lated by including the standard devia-
Since the numerical significance of the tions of the blank, slope, and intercept
analyte concentration increases as the in the equation. The statistical expres-
analyte signal increases above XL, a sions for these values are listed in
minimum criterion, representing the Table I.
ability to quantify the sample, can be Although these models require ad-
established reasonably far way from ditional calculations, most linear re-
ZB.This criterion, called the limit of gression analyses are performed using
quantification (LOQ), is 1Ou away calculators or microcomputers. With
from i i ~For
. limit of detection work, additional programming, these calcu-
u = ss. Samples that are measured as
lations can be easily performed, allow-
having a signal, x, where x > 1 0 8 ~are ing more accurate determinations of
termed tobe in the region of quantita- CL values to be made. These values
tion while samples where 3SB Q x Q may also be used for a truer compara-
1OSB are termed to be in the region of tive look at the ability of an analytical
detection. method or instrument to quantify
By setting the quantitation level as trace elements (or compounds) in a
loss or the identification limit as ~ S B , sample.
a much higher probability is afforded
that the sample signal is not just a
random fluctuation of the blank.
However, when making comparisons Graphical Approach
using LOQ or CI to IUPAC CL values, To obtain a more reliable CL value,
the analyst must bear in mind the dif- the m value should be expressed as a
ference in the kfactors for each limit. confidence interval m f t,s,, where
8, is the standard deviation of the

Methods Involving slope and t, is a t distribution value


Analytical Sensiilviiy Error chosen for the desired confidence
level, a,and the degrees of freedom, u.
The previous models for calculating The insertion of this interval into
detection limits consider the error in Equation 7 produces
the blank measurements. These mod-
els also consider the analytical sensi-
tivity, m, as a well-defined value. In
practice, however, m may have signifi-
cant error due to nonlinearity in the
calibration curve, or measurement er- The effect of the inclusion of the con-
rors. fidence interval can best be seen by
The following proposed detection referring to Figure 5. The error bars
limit approaches include errors associ- (confidence interval) generated
ated with measurements of the analyt- around the regression line are indicat-
ical
'
sensitivity.
. " ' The first method, a ed as white dashed lines. Because of
graphical approach, includes the stan- error in the slope, three concentration

710A ANALYTICAL CHEMISTRY, VOL. 55, NO. 7. JUNE 1983


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values are found for a given XL value.
When tasm = 0, (as in Equation 7), the
value of CL is obtained. However, the
reduced analytical sensitivity yields a
value, CR, to the right of CL. If
m >> tasm, then the CR will not be sta-
tistically different from CL. For the sit-
uation when tasm is not sufficiently
small as compared to m, a CR may be
aubstantially larger than CL, There-
fore, only the larger value should be
used in reporting a limit of detection.
An important consideration in the
me of this model is the choice of a
t value. The recommended k value of 3
involves a 99.87% confidence level,
Therefore, the t should reflect a simi-
ar level. An a = 0.0005 results in a
:onfidence level of 99.9% for a two-
;ailed t distribution. The degrees of
ieedom, u, are n - 2 for a linear re-
:ression model. The n value used
5hould be the number of points used
;o prepare the calibration curve, i.e.,
?achpoint consists of a mean measure
md a concentration value.

Propagationof Errors Approach


In the second approach used to
evaluate CL, the error in the intercept
term, i, as well as the error in m are
considered. To include these errors,
Equation 1must be rearranged to

From Equation 18,any value of x can


be related to a concentration using the
m and i values obtained from the lin-
ear regression model. The i term is
usually neglected in most cases and
sssumed to be 0 because the analytical
measures are background subtracted.
But in most linear regression analyses,
i # 0. If a true reflection of the error
in the determined concentration is
sought, the error in m and i must be
included in Equation 7.
The contribution of each term to
the total error may be found by taking
the first derivative of c with respect to
each term:

(3
+ - sm2
Taking the designated derivatives and
(19)

the square root gives

+ (- %)2sm2]1/2 (20)
and finally combining like terms
yields

s, =
[...+ si2 +(q2smj1/2
(21)
m

720A ANALYTICAL CHEMISTRY, VOL. 55, NO. 7, JUNE 1983


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poorly defined i value and a well.de.
fined m value; C, Cu(1) fluorescence
data where there is nonlinearity in the
calibration curve resulting in ill-de-
fined m and i values; and D, Co(II)
fluorescence data where extreme non-
linearity in the calibration curve re-
sults in severe errors in both m and i
values. The limit of detection values,
C L ( L = ~ ) for
, the three methods are tab-
ulated in Table 111. Here the C L ( ~= 3)
values are reported only to one signifi-
cant figure, as all CL values should be.
The subscript numbers representing
the second significant digit in cases A
and B are included only for compara-
tive purposes.
For case A, the IUPAC model and
the graphical approach agree well.
Only the propagation of errors model
shows a significantly higher C L ( =~ 3)
value; this deviation is the result of
the error associated with the intercept
value.
The values obtained in case B em-
phasize the problem of an ill-defined,
nonzero intercept. This problem is the
direct result of constructing calibra-
tion curves for detection limits when
the lowest point of the calibration
curve data is considerably removed
from the CL(k = 3) value. Only the
propagation of errors model accounts
for this error, while the other two
methods indicate an erroneously low
CL(k = 3) value. Although there are no
0.05 set guidelines for constructing calibra-
5 tion curves, the third approach clearly
illustrates the problem of sampling
too far away from the limit of detec-
tion.
In some instances, calibration
curves may not be linear. Although
the linear regression procedure will fit
Equation 21 allows the determination In the event that no significant a line through the data, the resulting
of standard deviation in a c value cal- error occurred in the slope, Equation m value is by no means a “true” repre-
culated from any x value. 21 reduces to sentation of the analytical sensitivity
In the case of limits of detection,
k[se2+ ~ i * ] ’ ’ ~ a t all concentrations. Nonlinear cali-
the EL value is actually a confidence CL = (24) bration curves generally produce sig-
value expression of how well the blank m
nificant sm, si, and i values. Case C
is known. If Equation 7 is reconsid- If the error in the intercept, si, is suffi- represents such conditions. The
ered, it can be written as ciently small, Equation 23 reduces to IUPAC model results in a CL(k = 3, of
Equation 7, which is the IUPAC defi- 0.03 ppm. Repeating the CL calcula-
CL = ks, (22) nition of the limit of detection. tion using the graphical approach re-
sults in a value of 0.3 ppm. Finally al-
-
where the S B h term describes the
error in terms of c (if c a), Equa-
tion 21 could now be used to evaluate
Evaluation of Approaches
The IUPAC, graphical, and propa-
lowing m and i errors to be included
results in a CL(k 3) of 5 ppm for the
gation of errors models will be applied propagation of errors method. The
se where x is the blank signal, jte, and to four different sets of experimental
SB is substituted for 9. By measuring
propagation of errors value is 170
data to show the effect of certain ex- times the IUPAC CL(k = 3) value.
ZB. SB,and calculating m, i,, ,s and si, perimental conditions on the estima-
the value of s, can be determined. The problem of nonlinearity can be
tion of CL values (Table 11).The data further emphasized by considering
In most determinations, the data in Table I1 have been taken from a re- case D. Here, the errors associated
-are background corrected, that is,
XB = 0. Substituting the above mea-
cent paper on ICP-excited ICP fluo- with m and i are greater; however, the
rescence detection limits ( I 5 ) .The large value of sm results in a special
sured and calculated values in Equa- four sets of typical experimental con- problem with the graphical approach.
tions 21 and 22, the expression for CL ditions are: A, Ca(I1) fluorescence If t,s, > m, then the concentration
is further simplified to data which have well-defined m and i value for the limit of detection can
values; B, Ca(I1) fluorescence data even be negative. Such negative values
where SB is essentially the same as in are the direct result of the graphical
A, but the calibration curve data are model not being statistically valid. Al-
taken far away from CL resulting in a though the graphical model is easier to

722A ANALYTICAL CHEMISTRY, VOL. 55. NO. 7, JUNE 1983


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use than the propagation of errors ap- References
proach, the former may give erroneous
(1) “Nomenclature.symbols. units and
results as seen in Case D. Thus, the their usage in spectrochemical analysis-
graphical method could be used only 11,” Spectroehim.Acto R l97R,33fl,242.
for approximating CL values. The de- (2) “Guidelines for Data Acquisition and
tection limit using the propagation of Data Quality Evaluation in Environmen-
tal Chemistry.” Anal. Chcm. 19RO.52,
errors approach is calculated to be 2242.
6 ppm. Correspondingly. the detection (3) Kaiser. H. “Two Papers on the Limit of
limit for the IUPAC model is 0.5 ppm, Detection of a Complete Analytical Pro-
differing hy a factor of 12 between the cedure”;Hafner: New York, 1969.
(4) Kaiser, H. Anal. Chem. 1970.42, (2).
two methods. 24 A.
( 5 ) Kaiser. H.Anal. Chem. 1970.42, (4).
Conclusions 26 A.
(6) Kaiser, H. Speetroehim.Acta R 1978.
Based on the above considerations, 33R. 551.
the graphical approach to CI, should (7) Houmans. P.W.J.M. Speetrochim.
not be used. The IUPAC approach is Acta R 1978,33R,625.
(8) Bournan!, P.W.J.M.; deBoer, F. J.
valid only if the major source of error Sperlroehrm.Acto R 1972.27R. 391.
is in the blank, i.e., SR* >> si*or sm2. (9)Houmans. P.W.J.M. “Lines Coinci-
Therefore, the IUPAC approach in dence Tables for Inductively Coupled
most cases gives artificially low values Plasma Atomic Emission Spectrometry”;
Pergamon: Oxford. 1980.
of CL. The propagation of errors ap- (10) Currie. L.A. Nurl. Imtrum. Methods
proach i s certainly the most liberal ap- 1972,100,387.
proach and will give values of CL con- (11) Glaser,J. A,; Fwrst. D. L.; McKee,
sistent with the reliability of the blank C. D.; Quave,S. A.; Budde, W. L.Enui-
Ion. Sri. Teehnol. l9Rl. 1.5, 1426.
measures and the signal measures of (12) Peters, D. G.; Hayes. J. M.; Hieftje,
the standards. C. M. “Chemical Separation and Mea-
We recommend that analysts report surements”;Saunderr: Philadelphia,
1974; Chapter 2.
limits of detection using the IUPAC (13) Winefordner. J. D. “Trace Analysis:
approach with k = 3 ( c L , ~ 3,). The Spectroscopic Methods for Elements”;
use of the propagation of errors ap- Wiley: New York. 1976; Chapter 1.
proach is also recommended because (14) “Nomenclature.symbols, units, and
errors in the analyte measurements their usage in spectrochemical analysis-
III.”Spcctrochim.Acto R 1978.33fl.
can be incorporated into the CL value. 248.
By adopting these approaches, mean- (15) Kosinski, M. A.; Uchida, H.; Wine-
ingful comparisons of analytical meth- fordner,J. D. Anal. Chem. 1983,5.5.688.
ods and instruments based on CL val- Thiswork wassupported by AF-AFOSR.
ues can be made. F49620-M-C.W05.

James D. Winefordner (1. ) is a gradu- ment of new instrumental methods


ate research professor in chemistry a t based upon new optical and detection
the University of Florida. His re- approaches; and applications of ana-
interests include diagnostical mea- lytical techniques.
surements of flames and plasmas;
laser-excited luminescence, pho- Gary L. Long is a postdoctoral asso-
toacoustic and photoionization of ciate in the department of chemistry
molecules in gases and liquids; laser- a t the Uniuersity of Florida. He re-
excited fluorescence of a t o m in ceived his RS in chemistry from Wake
flames and plasmas; development of Forest University in 1978 and his
trace analytical methods for atoms PhD in anolytical chemistry from
and molecules based upon lumines- North Carolina State University in
cence, chemiluminescence. pho- 1982. His research interests include
toacoustic, and ionization methods; ICP-excited ICP fluorescence spec-
specialized methods for molecules trometry, laser-excited flame fluores-
based upon synchronous lumines- cence spectrometry, and the investi-
cence, room-temperature phospho- gation of chemical and physical inter-
rimetry, energy transfer lumines-
P ~ I ~ P
ferences in flame and plasma spectro-
cence. and time resolution; deuelop- metric analyses.

724A ANALYTICAL CHEMISTRY. VOL NO. 7. JUNE 1983

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