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Detection limit and estimate of uncertainty of analytical XRF results

Article · January 2001

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THE RIGAKU JOURNAL
VOL. 18 / NO.2 / 2001

DETECTION LIMIT AND ESTIMATE OF UNCERTAINTY OF

ANALYTICAL XRF RESULTS*

DR. RICHARD M. ROUSSEAU

Geological Survey of Canada, 601 Booth St., Room 707, Ottawa, Ontario, K1A 0E8 Canada. e-mail: [email protected]

Some tools for estimating the uncertainty of XRF results are described. As introduction to the subject, the detection
limit is treated even if this parameter and the uncertainty of a result describe different characteristics of an analytical
method. The expression "detection limit" is probably one of the most widely misunderstood in XRF analysis. Not
only is there a general lack of agreement about the order of magnitude of detection-limit data, but also the interna-
tional convention for calculating such data is not always respected and the way of naming them is questionable. If a
consensus exists on the meaning of this expression (the smallest amount of an analyte that can be detected in a
specimen), the interpretation of data varies greatly. This paper attempts to suppress all this confusion. The basic
philosophy behind the interpretation of the concept is reviewed and a new realistic and representative way to name
it is proposed. The distinction between the limit of detection and the limit of determination is clearly established.
General considerations for evaluating the uncertainty associated with the sample preparation are also discussed.
Finally, a few comments on the way of reporting analytical results are presented.
on the combination of errors introduced mainly by
1. Introduction'
the sample preparation, the measurement of both
The basic requirement of quantitative X-ray
peak and background intensities, the slope "m" of
fluorescence (XRF) analysis is first to prepare suit-
the calibration line and the corrections for matrix
able specimens from the samples to be analyzed.
effects. All these errors can be grouped in two
Then, to measure the intensity Ip of the peak of the
main categories. The first one is the random error,
element to be determined (or analyte) since this
represented by the precision, which can arise, for
intensity is related to the concentration by means
example, from random fluctuations associated to
of the calibration procedure [1]. However, this ana-
the process of measurement of X-ray peak intensi-
lyte peak intensity must be first corrected for dead
ties.
time, which is normally done automatically by
These are called counting statistical errors [3]
contemporary instruments. If necessary, particu-
(CSE). The other category is the systematic error,
larly for trace element determination, it must also
represented by the accuracy, whereby a certain bias
be corrected for background beneath the peak, any
is present in the results, as could happen if a badly
spectral overlap(s) and blank. Finally, if necessary,
determined calibration curve is used. Precision can
the net intensity must be multiplied by the term Mis
be considered as a measure of the repeatability
to correct for matrix effects [2]. However, a de-
[4,8] (replicate determinations made under condi-
scription of this last step, and also calibration pro-
tions as nearly identical as possible) of a result,
cedures, will be ignored in the present paper on the
while accuracy is a measure of the closeness of the
uncertainty associated with analytical XRF results,
results with its true value. As an analogy, if we
that having already been treated in other papers [1,
have a ruler with an incorrectly engraved scale, we
2]. We will consider, instead, how to estimate the
could repeat with precision the measurement of the
uncertainty introduced in the analytical results dur-
length of an object, but the results will be inaccu-
ing all these steps. .
rate. The combination of these two types of errors,
In quantitative XRF analysis, the global (or
precision and accuracy, enables us to estimate the
overall) uncertainty of an analytical result depends
global uncertainty of each concentration to be de-
'
Certain instrument manufacturers are identified in this termined. In practice, precision can be improved
paper to specify adequately the source of experimental by controlling the random errors introduced during
data. Such identification does not imply recommenda- sample preparation and by the analytical instru-
tion or endorsement by the author, nor does it imply that ment within the range of stability of the generator
the instruments used are necessarily the best available and of the X-ray tube, to such an extent that the
for the purpose. main source of random errors remaining is due to

Vol. 18 No. 2 2001 33

counting statistical errors. Accuracy can also be for evaluating the uncertainty associated with the
improved to a large extent by controlling system- sample preparation will also be discussed. Finally,
atic errors introduced by sample preparation, the few comments on the way for reporting analytical
instrument itself and the calibration procedure. results are presented. The analysts must absolutely
These errors can be reduced within certain limits employ an explicit way of reporting results and
by optimizing the use of the analytical instrument assessing the capabilities and limits of the analyti-
and by improving the reliability of the calibration cal method.
procedure. As a result, only residual systematic The present paper is not a proposal for a new
errors due to the specimens themselves are then terminology or new mathematical definitions for
important, which are matrix effects (absorption and calculating detection limits applicable to all ana-
enhancement) and physical state effects (heteroge- lytical techniques, but rather to show how the
neity, surface, thickness, particle size, mineralogy). complex jargon of statisticians, often disconnected
This paper deals mainly with the uncertainty intro- from the physical reality, should be adapted to the
duced in a series of results by the random and sys- field of XRF analysis. We are more interested to
tematic errors of all the mentioned sources. Some supply to the XRF analyst the necessary tools for
tools will be described hereafter for estimating this evaluating the quality of her/his results rather than
global uncertainty. getting international recognition. For a more gen-
However, the first subject to be treated is the eral and thorough discussion on the subject, you
detection limit in spite of both parameters, uncer- may refer to the paper by the International Union
tainty of a result and detection limit, describe dif- of Pure and Applied Chemistry (IUPAC) [6]. This
ferent characteristics of an analytical method. This paper also contains other interesting references,
first preliminary step is necessary for evaluating which are not repeated here.
the total performance of an analytical system. It is
2. Sensitivity of an Instrument
also important to talk about this parameter because
An important tool needed for the determination
the expression "detection limit" is probably one of
of the three limit types is the sensitivity of an in-
the most widely misunderstood in XRF analysis.
strument for a given analyte in a given specimen. It
Not only is there a general lack of agreement about
is defined as being the net intensity obtained per
the order of magnitude of detection-limit data, but
unit of concentration. For calculating it, the peak
also the international convention for calculating
intensities of the analyte have to be measured on
such data is not always respected and the way of
certified reference materials (erroneously known in
naming them is questionable. The detection limit is
popular language as standards) of composition
usually defined as the smallest amount of an ana-
similar to that of the unknown samples to be ana-
lyte that can be detected in a specimen. However,
lyzed. To calculate the sensitivity, the measured
it is often misinterpreted as the smallest concentra-
intensities must not be corrected for matrix effects
tion of an analyte that can be determined with reli-
and one must assume a linear relation between in-
ability in a given sample. Furthermore, the detec-
tensity and concentration. The sensitivity for each
tion limit calculations are based on background
anaIyte i is calculated from the slope mj of the cali-
measurements, which are below any peak intensity
bration line as follows. The general form of the
used for a possible determination. This paper at-
equation for a straight line is
tempts to clarify all this confusion. The basic phi-
Y = mX + b (1)
losophy behind the calculations of the different
If the calibration line is a plot of the peak intensity
limit types is reviewed and a new realistic and rep-
Ip of an analyte i as a function of the concentration
resentative way to name them is proposed. It must
Ci, the equation (1) becomes
be emphasized that the terminology used here is
Ip = miCi + Ib
presented to prevent ambiguity, but does not have
where the true background intensity Ib is given by
any international ratification. Potts [5] has already
the intercept of the calibration line on the Yaxis.
tried to do this, but without much success.
The slope mi is then given by
Three types of limits are considered: the in-
I p − Ib
strumental limit of detection, the limit of determi- mi = (2)
nation of a method and the theoretical or experi- Ci
mental analytical precision. General considerations

34 The Rigaku Journal

where Ci is the concentration of the analyte i in % the LLD expression makes no sense.
or ppm. It is the slope of the calibration line that Secondly, the LLD is defined as being the
enables to convert measured net intensities into lowest net peak intensity of an analyte, expressed
concentrations. in concentration unit, that can be detected by an
instrument in a given analytical context with a 95%
3. Instrumental Limit of Detection
confidence level. This minimum intensity is as-
An important statistical consideration in XRF
sumed to be equivalent, for a 95% confidence
analysis is the capability of an instrument to
merely detect whether an element is present or not level, to two standard counting errors (σb) of a set
in a specimen. In fact, one wants only to be able to of measurements of the background intensity (Ib)
claim with some defined statistical certainty that a under the analyte peak [7], i.e., in terms of inten-
given element is present if its concentration is sity, assuming no error in the time of the back-
greater than a certain limit. This limit is the limit of ground measurement (Tb):
detection. This last limit is much smaller than, Ib
even under the best analytical conditions, the limit
2σ b ⇒ 2 ⋅
Tb
of determination that is the smallest concentration
that can be determined (or quantified) with reliabil- and in terms of concentration:
ity in a sample (more on this subject in Section 5). 2 I
When an XRF analyst develops a new analyti-
2σ b ⇒ ⋅ b
mi Tb
cal program, she or he must calculate the smallest
concentration of the analytes that can be detected where mi is the slope of the calibration line or the
in a specimen to check if the instrument is sensi- sensitivity of the spectrometer in cps/% for an ana-
tive enough to detect all the concentration range of lyte i. When two measurements are required, as
the elements to be determined. The most current with XRF analysis where it is frequent to have to
detection limit used in XRF analysis is the lower measure peak and background intensities, the error
limit of detection, which is assumed to be the con- is increased by a factor 2 , so the lower limit of
centration equivalent to three standard counting detection is equal to
errors [3] (σb) of a set of measurements of the 2 × 2 Ib 3 I
background intensity [7]. It will be shown that this LLD = ⋅ ≈ ⋅ b (3)
limit IS an over-optimistic estimate of true limits
mi Tb mi Tb
of detection met in practice mainly favored by in- or replacing mi by the equation (2), it comes:
strument manufacturers and that should be aban- 3 × Ci I
doned [5]. LLD = ⋅ b (4)
The expression "Lower Limit of Detection"
I p − I b Tb
(LLD) is often used in X-ray literature to represent Thus, the current LLD used by manufacturers is
the smallest amount of an element in a given equal to three times the standard counting error of
specimen that can be detected by an instrument in the background intensity. The "fictitious numbers"
a specific statistical context for a given matrix. It is calculated by the expression (3) or (4) are not rep-
unfortunate that many analysts use this limit in resentative of the limits of detection met in prac-
practice for the three following reasons. tice. It is important to emphasize that the LLD is
Firstly, there is no such thing in real life like not representative of true experimental results but
the LOWER limit of detection or HIGHER limit of only of a minimum theoretical estimation. Quan-
detection or any other unrealistic term to qualify titative analysis is not possible at the LLD level for
the expression "Limit of Detection". For example, the following reasons. Because the number of real
when a car, a plane, a helicopter, a train, etc., measurements is always limited to a finite number,
reaches its maximum speed limit, it cannot travel the uncertainty in the mean background intensity,
any faster. A limit is a limit. The association of the measured on a blank specimen, is assumed negli-
word "lower" with the expression "limit of detec- gible and the experimental standard deviation Sb is
tion" is redundant, a non sequitur! It is like saying estimated by the theoretical standard counting error
lithe lowest low limit". Their combination is ir- σb. Now, σb is calculated from measurements that
relevant and meaningless. In practical situations, are assumed to respect to the letter statistical rules.

Vol. 18 No. 2 2001 35

In practical situations it is unrealistic to assume tection limit.
that such measurements will exactly follow a The limit of detection is related to the capabil-
Gaussian (or normal) distribution [3]. Also, a de- ity of the instrument to distinguish a peak intensity
tection limit calculated with a 95% confidence (Ip) from the fluctuations of the background inten-
level (2 σb) is not usually considered to afford suf- sity (Ib) due to counting statistics, or the back-
ficient security of confidence for analytical meas- ground noise. The question then arises: «What is
urements. Finally, the background counting time the lowest peak intensity of an analyte that can be
(Tb) is often replaced by the total time (n to meas- measured to be recognized as distinct from the
ure the peak and background (where T=Tp+Tb and background noise?» If a large number of meas-
Tp= Tb= T/2) and the value used in this case by urements of a background intensity Ib is made, all
most instrument manufacturers is 100 s. The only measurements are subject to counting statistical
reason for doing that is obviously to reduce still errors and fluctuate around a mean value I b . Thus,
more the LLD value, which decreases when the many repeated measurements of a background in-
counting time increases. All these "artifices" have tensity will result in a distribution of data that ap-
only as objective to make fictitious numbers look proximates to a Gaussian (or normal) distribution
better, not to better represent the reality.
Thirdly, the meaning of the lower limit of de- characterized by a mean value I b and a standard
tection is most of the time completely misunder- counting error [3, 5] σb. Thus, the standard count-
stood. A limit of detection is not a limit of deter- ing error σb represents the fluctuations of Ib due to
mination. The expressions "limit of detection", counting statistics, or the background noise.
which is based on background measurements and Furthermore, the XRF analyst must select the
"limit of determination", which is based on the confidence level to associate with any assertion
measurement of any peak intensity above the that the analyte is present in the specimen. For ex-
background are often misused and frequently inter- ample, a 95% confidence level means that, for a
changed, which is a big mistake. In other words, large number of observations, 95% of the observa-
the smallest concentration of an analyte in a given tions indicate the presence of the analyte, whereas
sample that can be determined by an instrument 5% of these observations reflect only random fluc-
cannot be estimated from the measurement of only tuations in background intensity. However, ninety-
the background intensity. It takes at least the five percent is an insufficient confidence level to
measurement of a characteristic line to be able to be sure that any measured intensity is distinct from
determine the value of this concentration. the background noise. That is why the value rec-
We suggest replacing the artificial expression ommended by IUPAC [6] is 99.95%.
LLD by another more realistic one with a different In practical analytical situations, a characteris-
name, a different definition and calculated by a tic line intensity Ip decreases with decreasing con-
different mathematical expression in order to make centration of the analyte and finally disappears in
it more representative of the reality. We suggest the background noise in the case of a blank sample
using the expression Instrumental Limit of Detec- (see the position 0 of Fig. 1). To be significantly
tion (ILD), which is defined as being the minimum different from the background, the peak intensity Ip
net peak intensity of an analyte, expressed in con- must not only be larger than I b , but also be statis-
centration unit, that can be detected by an instru-
tically distinguishable from the background noise.
ment in a given analytical context with a 99.95%
confidence level. The ILD depends on the instru- Based on Gaussian distribution statistics [3], the
probability that the analyte to be present is 99.95%
ment, the specimen matrix composition and the
analyte. But the reading by different instruments of if the peak intensity Ip is larger than ( I b +3.29σb)
the same element peak in the same specimen, and [6]. In this case, the probability that a background
in the same experimental conditions, will give dif- measurement may exceed ( I b +3.29σb) is only
ferent ILD values. It does not depend on the
0.05%.
mathematical method used to calculate concentra-
tion values. For a given analyte in a given speci- Any peak intensity will be detected with a con-
men, the ILD depends only on the instrument. That fidence level of 99.95% when higher than ( I b +
is why we suggest calling it the instrumental de- 3.29σb) and will not be detected, for the same

36 The Rigaku Journal

level of confidence, when smaller than ( I b + I net ≥ 3.29 2σ b2 = 3.29 2σ b ≅ 4.65σ b
3.29σb). The decision "detected" or "not detected" The ILD is the concentration corresponding to Inet,
is thus established by comparison to a threshold, or i.e.,
a limit of detection, which is the combination of
4.65 I b
the mean background intensity and the background ILD = (5)
noise. The ILD represents then a threshold above mi Tb
which a peak intensity can be distinguished from This approach yields minimum detection limits in
the background noise at a specified level of confi- terms of concentration that can be observed under
dence. Under this threshold the peak intensity is the best analytical conditions. Conveniently, we
assumed to be indistinguishable from the back- have a 99.95% confidence level to distinguish a net
ground noise. intensity from the background noise if this net in-
In XRF analysis, any concentration is calcu- tensity is larger than a "fluctuation" of 4.65σb
lated from the net peak intensity (Inet, which is above the mean background intensity. It is still a
equal to the difference between the measured peak minimum theoretical estimation but the chances
intensity (Ip) and the background intensity (Ib). are better (as compared to the LLD) to detect it in
However, there is a standard counting error (σp) practice.
attached to any measurement of the peak intensity. The instrumental limit of detection is only use-
Likewise, any measurement of the background in- ful to the analyst for estimating the lowest net in-
tensity is also accompanied by a standard counting tensity, expressed in concentration unit, that can be
error (σb). Therefore, the XRF analyst is con- detected by an instrument. This value is not equal
fronted with the problem of distinguishing the true to and is in fact much lower than the smallest con-
net peak intensities from the random fluctuations centration of the analyte that can be actually de-
in peak and background intensities. To calculate termined by the instrument. It is important to em-
the limit of detection in terms of net intensities, phasize that fact. In practice, this limit is used only
first, let us remind ourselves that the variance [3] for checking if the instrument is sensitive enough
of the sum of (or the difference between) two val- to detect all the concentration range of the ele-
ues taken from statistically independent distribu- ments to be determined in a particular sample type.
tions is equal to the sum of the variances of the two This limit can also be used for comparing the per-
distributions. Thus, for net intensities, formance of different instruments used in the same
σ net
2
= σ 2p + σ b2 analytical context. It must never be given to the
customer submitting samples for analysis who may
where σnet is the standard counting error of the net
confuse it with the smallest concentration of the
intensity for the peak of interest.
analyte that can actually be determined.
We can ask, «What must be the minimum
The real physical meaning of the instrumental
value of the net peak intensity to be sure (or
limit of detection is shown by Fig. 1. Suppose that
99.95% sure) that we are not merely measuring the
a series of samples containing a trace element at
statistical fluctuations of the background inten-
different concentration values is prepared where
sity?» The answer is that the net intensity must
the concentration decreases, from sample to sam-
exceed 3.29 times the standard counting error of
ple, from a given value to zero. The intensities of a
the net intensity, otherwise, there is at least 0.05%
line are measured and decrease with the decreasing
of chance that the measured net intensity arises
concentrations of this element from the position 18
merely from statistical fluctuations in peak and
to the position 0, which represents a sample that
background intensities. This requires that
does not contain any concentration of the element.
I net = 3.29σnet
At this last position, no peak is measured, but only
The combination of the two last equations gives:
the background, because the element is absent
I net ≥ 3.29 σ b2 + σ 2p from the sample. We have reached the point at
or, assuming that the measured intensities are close which a peak intensity is indistinguishable from
to their respective means and that, for very small the background noise. At this position, we are far
below the "limit" (or the threshold) of detection,
net peak intensities, Ib»Inet, or Ip˜ Ib, or σp˜ σb,
which is located at 4.65σb above the mean back-

Vol. 18 No. 2 2001 37

ground intensity with a confidence level of counting time on peak (Tp) and background (Tb).
99.95%. Since at the detection limit, Ip˜ Ib, thus Tp˜ Tb˜ T/2.
The statistical meaning of the instrumental Thus Tb in equation (5) is one half of the available
limit of detection is as follows. Let us suppose that total counting time. Equation (5) can then be writ-
the peak and background intensities of an analyti- ten as follows:
cal line are measured and the calculated value of 4.65 Ib 4.65 × 2 × Ci I
the ILD gives for example 3 ppm. If these meas- ILD = ⋅ = ⋅ b
urements are repeated in exactly the same analyti- mi T 2 I p − Ib T
(7)
cal context, one can assume with a 99.95% confi-
6.58 × Ci I
dence level that the new ILD value will be in an ≈ ⋅ b
interval of ±4.65σb, in equivalent concentration I p − Ib T
unit, of the first calculated value. The author con- By selecting the optimal counting time split on
fesses that he cannot do the calculation here of σb peak and background, the relative counting error
but he knows enough to say that the 4.65 σb value [8] on the net intensity is calculated by
will be more than 3 ppm. Let us say to be conser-
vative that it is equal to 3 ppm. The new ILD value (ε % )net = 100 ⋅ 1
(8)
T I p − Ib
will be therefore between 0 and 6 ppm. The ILD
value means nothing else statistically. Any other A consequence of the equation (8) is that, as the
interpretation of this limit would be wrong and peak intensity (Ip) approaches the background in-
disconnected from reality. For example, saying that tensity (Ib), the net relative counting error becomes
the limit of determination is equal to 6 times the infinite. Now, this is precisely what happens at or
standard deviation of the background measure- near the detection limit: Ip is getting close to Ib.
ments is completely arbitrary and unfounded. Consequently, reliable measurements close to the
Note that the instrumental limit of detection detection limit level become "an impossible
defined by the equation (5) is associated to a dream…” as so well said by the famous song of
99.95% confidence level (or 4.65 σb) and that the Jacques Brel.
total measurement time T is equal to 2Tb. This fol- Note also from equation (7) that, for a fixed
lows from the following equation [8]: counting time, the ILD will be smallest when the
expression
Tp Ip
= (6) I p − Ib
Tb Ib (9)
Ib
which allows to calculate the optimal split of

Fig. 1. If the concentration of an element decreases from sample to sample, at some

point we cross the limit of detection located at 4.65σb above the mean background in-
tensity for a 99.95% confidence level, and we reach the point 0 where the peak is in-
distinguishable from the background noise (from Philips Analytical X-ray).

38 The Rigaku Journal

is as large as possible, For this reason, Spielberg The ILD also varies with the specimen matrix
and Bradenstein [9] proposed the equation (9) as composition. In general, for a given analytical con-
the definition of Figure of Merit (FOM), which is text, and for a given concentration of a given ana-
mainly used to optimize excitation conditions for lyte, the ILD will be smaller when the matrix com-
trace element determination. position becomes lighter. One observes this phe-
As a numerical example, if a given element at nomenon simply because the degree of absorption
a concentration of 0.2%, gives a peak intensity of decreases with light matrices and, therefore, the
330 cps and a background of 30 cps, for a total measured intensity is higher from samples with
counting time of 120s, the ILD is: light matrices. As an example, Table 1 lists a few
4.65 × 0.2% 30 ILD data for some low atomic number (Z) ele-
ILD = ⋅ = 0.0022% = 22 ppm ments. It can be seen that the ILD varies not only
330 − 30 60 with Z of the analyte but also with the specimen
An ILD of 22 ppm does not follow, however, that matrix composition. Taking Mg as an example, as
one could in practice determine 22 ppm of the the background intensity for Mg in Al metal is 7.8
element. This value is just a theoretical estimation times greater than that in limestone, the ILD is
of the lowest net intensity, translated in concentra- only marginally higher by a factor of 1.3. Also for
tion unit, that the instrument can detect with a sta- P in oil and nylon, an increase in background in-
tistical certainty. Furthermore, as it has already tensity by a factor of 35 results in an increase in
been pointed out, at or near the detection limit the ILD by a factor of only 2.5.
error becomes infinite. For these reasons, the theo- The ILD also varies with the atomic number
retical limit of detection is a somewhat arbitrary or (Z) of the analyte and the slope of the calibration
artificial concept and "meaningless" from an ana- line. ILD values may change with different X-ray
lytical viewpoint. A limit more useful in practice is tube anodes, mainly because the sensitivity factor
the one defined by the limit of determination of a will be affected by how efficiently the characteris-
method (LDM). This last concept will be explained tic lines of the tube excite the element(s) of inter-
in Section 5. est, but the final conclusion will stay the same: the
It is unfortunate that among beginner users the ILD varies with the Z of the analyte. For illustrat-
following popular belief is largely held: ing it, let us take a given X-ray tube anode and di-
uncertainty = analytical result ± ILD vide the periodic table in three wavelength regions.
i.e., that the uncertainty of a reported analytical The short wavelength region (0.3-0.8 Å), i.e., for
result (% or ppm) is within the ILD limits in Zr (40) to Ba (56), is characterized by a moderate
99.95% of the cases. This belief is misleading and slope value, high background and excitation condi-
in no case it can be true. tions far from optimum, which lead to moderate
From equation (5), it can be deduced that the ILD values. The medium wavelength region (0.8-3
limit of detection decreases as the background in- Å), i.e., for Ca (20) to Zr (40) for K lines and for
tensity decreases, as the slope of the calibration Ba (56) to U (92) for L lines, is characterized by a
line increases and through longer counting times. high slope value, low background and optimum
excitation conditions, which lead to the best ILD
Table 1. Instrumental detection limits for low
atomic number elements. The ILD is calculated for values. The long wavelength region (3-12 Å), i.e.,
the 99.95% confidence limit with 100 s as total for Na (11) to Ca (20), is characterized by a small
counting time. Data taken from Ref. [10]. slope value, low background and the poorer excita-
Element Matrix mi Ib ILD tion conditions, which lead to the poorest ILD val-
(cps/%) (cps) (ppm) ues [10].
Na Al2O3 108 42 395 Thus the ILD varies with the matrix composi-
Mg Limestone 646 60 79 tion of the specimen and with the atomic number
Mg Al 1360 470 105 of the element to be determined. It means that the
Si Steel 2300 105 29 ILD determined from a specimen is valid only for
Si Limestone 2950 90 21 this specimen and any other determination of the
P Oil 24000 450 6
same element in other specimens, with different
P Nylon 10000 13 2.4
S Oil 63000 170 1.4 matrix compositions, will lead to different values
of ILD. The analyst must be aware that the ILD is

Vol. 18 No. 2 2001 39

equivalent to a pure hypothetical and theoretical it must be calculated for each analyte and for each
concentration value, which will probably never be sample to be analyzed in a given analytical con-
determined in practice; or if measurements can be text.
made down to the detection limit, uncertainties To calculate the experimental analytical preci-
would normally be regarded as unacceptable. sion (EAP), repeat the measurement of the net in-
tensity of the analyte between 10 and 15 times on
4. Theoretical and Experimental Analytical
the same specimen, in the same analytical context,
Precision
and calculate the standard deviation of the distribu-
Two other useful limits to estimate the preci-
tion of measurements in terms of concentration
sion of the analytical process are the theoretical
unit for a 95.4% confidence level from the follow-
and experimental analytical precision. The theo-
ing expression:
retical analytical precision is used especially for

∑ (I −I)
n
trace element determination to check whether the 2
differences in concentration from sample to sample 2 m

are significant. The experimental analytical preci- EAP = m =1

(11)
sion is calculated when the analyst wants to evalu-
mi n −1
ate the quality of the sample preparation (see more where Im is the mth measurement of the net inten-
information at the end of Section 5). Note that both sity of the element i and I is the mean value of the
analytical terms are part of commonly used termi- n measured values of the net intensity. This ex-
nology and have not received international (ISO) perimental value (EAP) enables us to estimate the
approval. They have the merit, however, to apply random errors due to the instrument and counting
in an elegant and practical way some definitions statistics. It does not take into account the variabil-
recognized by ISO, such as the Poisson distribu- ity introduced by the sample preparation. As the
tion, standard deviation and repeatability (preci- instrumental precision should be negligible for
sion) [4]. modern instruments, the experimental value (EAP)
The theoretical analytical precision (TAP) of should not differ of the theoretical value (TAP) by
an element in a given specimen, determined by a more than 50%. If it is the case, then there is an-
given analytical method, is the concentration other error source than counting statistics (for ex-
equivalent to two standard counting errors on the ample, the instability of the instrument). It must be
net intensity of the analytical line. The TAP is a investigated, found and corrected.
theoretical estimation of the precision of peak and
5. Limit of Determination of a Method
background measurements, expressed in concen-
Regarding the determination limit concept,
tration unit of the analyte, that does not take into
there is a very significant difference between the
account the random errors introduced by the in-
terms detection and determination. The limit of
strument and the sample preparation.
detection is a theoretical estimation of the lowest
To determine it, measure for each specimen,
net intensity that can be measured (or detected) by
peak and background intensities of the element of
an instrument from a given specimen at the peak
interest by applying the complete procedure of
position of a given anaIyte, with a specified level
measurement.
of confidence. This last limit is much smaller than,
The theoretical analytical precision (TAP) ex-
even under the best analytical conditions, the limit
pressed in terms of concentration unit for an ele-
of determination that is the smallest concentration
ment in a given specimen, to be determined by a
of an analyte that can be determined (or quantified)
given analytical method, is calculated by
with reliability in practice in a given analytical
2 I p Ib context.
TAP = × + (10)
Statisticians usually define the limit of deter-
mi T p Tb
mination as six times the theoretical standard
where the sensitivity mi is calculated by the equa- counting error above the mean background inten-
tion (2). This TAP value is valid only for the ana- sity (Ib+6σb) [5, 6]. It cannot be quantified, how-
lyte i in the specimen used for determining it. It is ever, only from the measurement of the back-
used to evaluate if the differences in concentration ground intensity Ib. To do so can be extremely mis-
from sample to sample are significant. In this case, leading. The correct quantitative definition must

40 The Rigaku Journal

take into account the level of confidence and the n

distribution of data as influenced by factors such as ∑C m

the repeatability of the sample preparation, the in- C= m =1
(13)
strument, the type of matrix to be analyzed, the n
calibration procedure, the analytical method and The LDM value calculated using the equation (12)
the analyte concentration range. The author under- will, for a particular element, vary according to the
stands precisely why the above definition has been concentration present in the specimen on which
proposed [5, 6], but have to respectfully disagree measurements are made. It is why the selected
with it and its use should even be discouraged. The sample must be representative of the series of sam-
traditional definition of the determination limit ples to be analyzed. A good practice is to select a
(Ib+6σb) is not representative of the smallest con- sample containing the mid-value of the calibration
centration of an element that can be determined in range of the analyte.
practice in a given analytical context. Indeed, it Equation (12) calculates the standard deviation
makes no sense to claim that the determination of the distribution of a series of calculated concen-
limit for an element is only 2 ppm when the result trations. A 95.4% confidence level is associated to
cannot be reproduced better than ±20 ppm. this standard deviation. This means that there is a
As opposed to the limit of detection (ILD) and probability of 95.4% that, if the determination of
the statisticians' definition of the limit of determi- the analyte is repeated using the same analytical
nation (Ib+6σb), which give the "illusion" that the method, the new concentration value will be within
performance of an instrument is better than it is in the limits of the LDM value, i.e., between the re-
reality, the limit of determination of a method sult ± the LDM value. On the other hand, this does
(LDM) is defined as the smallest concentration of not guarantee in no circumstance the accuracy of
an analyte in a given sample that can be reliably this concentration value. We will come back on
quantified in practice by a given analytical method this subject in Section 7.
with a 95.4% confidence level. In practice, a con- For the XRF analyst, the LDM represents the
fidence level of 95.4% is enough. Our definition minimum concentration that can be determined and
for calculating the limit of determination enables reported with a specific level of confidence. This is
us to estimate in practice how well an analytical the only limit that should be reported to customers
method can repeat a given result. It takes into ac- with every determination. The determination limit
count the errors introduced by the sample prepara- is particularly useful for the determination of trace
tion, instrument and counting statistics. It is the elements. If it is unknown, there is a serious risk of
smallest uncertainty introduced by an analytical reporting meaningless analytical results when they
method taken as a whole. It is this uncertainty that are below the determination limit. For geochemical
must be given aside of any analytical result with determinations, where many varieties of matrices
the famous "plus-or-minus" (±), as for example are analyzed, it is even appropriated to calculate
0.022% ± 0.002%. We quantitatively define the subdetermination limit data, otherwise the statisti-
limit of determination of a method as the concen- cal assessment of only one set of data to all matri-
tration of an element equivalent to two standard ces will be biased.
deviations of a set of determinations of the same There is no theoretical concept that enables us
representative concentration. It is calculated from a to pretend that the limit of determination of a
series of n replicate specimens (n = 10) prepared method can be defined by the equation (12). We
from the same representative sample in the same were looking for a limit that was taking into ac-
experimental conditions. For a given element, we count the sample preparation and, based on our
have experience, was representative of the analytical
reality of a given XRF laboratory. The choice of
∑ (C −C)
n
2 equation (12) is based on the fact that it is reason-
m
able to think that the LDM is reached when the
LDM = 2 ⋅ m =1
(12) coefficient of variation [8] is 100%. Note that this
n −1
definition of the LDM is purely a suggestion. An-
where the mean concentration value is given by
other coefficient of variation of 200% could easily
be chosen. Our definition has at least the merit to

Vol. 18 No. 2 2001 41

be a practical scientific approach, at the limit be- Limit" has no other possible meaning than the ana-
tween a theoretical and empirical approach, rather lytical determination of an analyte in samples. Fi-
than to purely and simply claim that it is 6 times nally the limit of quantitation is superfluous. The
the standard counting error of the background two other limits as defined by us, detection and
measurements [5, 6] above the mean background determination limits, are sufficient to determine the
intensity ( I b +6σb). capabilities of an analytical system.
As the ILD, the LDM varies with the specimen
One frequently finds in literature [5, 6] the ex-
matrix composition, the atomic number (Z) of the
pression "Limit of Quantitation" as proposed by
analyte and the analytical context. However con-
the American Chemical Society Committee on En-
trary to the ILD, the LDM varies also with the
vironmental Improvements (1980) and set at a
level of the concentration of the considered analyte
level 10σb above I b . It is supposed to represent the in the selected testing sample. It is then very im-
smallest concentration of an analyte that can be portant, for calculating the limit of determination
quantitatively determined. In many practical ana- of a method, to select a real representative sample
lytical situations, this theoretical definition gives a of the series of samples to be analyzed. Table 2
false result. That is why its use is not recom- compares the ILD and the LDM of different ele-
mended. Furthermore, the expression ments in different certified reference materials.
"Limit of Quantitation" is ambiguous by itself. Furthermore, a comparison of results obtained
There are many parameters that can be quantified with equations (11) and (12) enables one to evalu-
in XRF analysis and when this expression is used it ate the quality of the sample preparation. Indeed,
is not obvious that we are talking about the quanti- from the addition law of the variance [3], the total
fication of the amount of an analyte in samples. On standard deviation is equal to
the other hand, the expression "Determination
s total = s 2prep + s inst
2
+ s stat
2
(14)
Table 2. Comparison of the Instrumental Limit of Modern instruments are stable enough for one to
Detection (ILD) and the Limit of Determination of a assume that the standard deviation sinst due to the
Method (LDM). X-ray tube: Rh Tube (s.w.). Speci- instrumental errors (generator, tube, crystal, detec-
mens: fused disc, 1 g sample+5 g Li2B4O7+0.3g LiF.
tor, goniometer, specimen chamber, etc.) is negli-
The ILD and LDM have been calculated for a 95.4%
confidence level and for a background counting time gible compared to sPrep and sStat. Then sInst˜ 0 and
of 100s. s Pr ep = stotal
2
− s stat
2
(15)
Element Z Reference Concentra- ILD LDM
material tion (ppm) (ppm) (ppm) where the total standard deviation sTotal is calcu-
S 16 BCR-1 400 3.9 267 lated by the determination limit (Eqn 12) and the
Cl 17 NS-1 500 0.4 standard deviation sStat due to the counting statisti-
Sc 21 BX-N 60 8.0
Cr 24 BR 380 9.8 20 cal errors is calculated by the experimental analyti-
Co 27 NIM-D 210 6.6 cal precision (Eqn 11). The standard deviation sprep
Ni 28 NIM-D 2050 5.1 43 represents the level of variability introduced by the
Cu 29 GSD-3 175 2.7 24 sample preparation and should never exceed 0.5%
Zn 30 SY-2 250 2.9 19
Ga 31 BX-N 70 2.7
in relative value. Its relative value should be ide-
Rb 37 SY-2 220 1.3 7 ally around 0.1% or 0.2%. This subject will be ex-
Sr 38 SY-2 275 1.3 19 plained in more detail in the next section.
Y 39 SY-2 130 1.0 4
Zr 40 SY-2 280 1.0 9 6. The Uncertainty Introduced by Sample
Nb 41 STM-1 270 1.2 5 Preparation
Mo 42 GSD-3 93 1.7 With modern instruments, it is possible to "iJ,]
Ba 56 GSP-1 1300 27.6 34 control the different sources of errors that
La 57 BX-N 390 18.3
Ce 58 GSP-1 360 14.8 originate from the instrument and the method of
Nd 60 GSP-1 190 10.7 concentration calculation. Indeed, random errors
Pb 82 GSD-7 350 3.1 18 due to instrumental and operational errors can be
Th 90 SY-2 380 2.3 minimized. The counting statistical errors usually
U 92 SY-2 290 2.8
can be made very small by selecting appropriate
counting times. Regarding systematic errors, they

42 The Rigaku Journal

can be greatly minimized when the instrument is Table 3. Comparison of the results of 1 measurement
operated by an experienced analyst, the composi- on 10 different fused disc specimens and of 10 meas-
tion of reference materials is accurately known and urements on the same fused disc. Data taken from
the matrix effects are corrected effectively. Ref. [11]
10 fused discs 1 fused disc
Finally, the last and most important source of 1 measure- 10 measure-
ment/disc ments
errors that must be eliminated, or at least reduced Mean intensity (cps) 213,110 212.996
as much as possible, is due to sample preparation. Total standard deviation (cps) 585 185
The uncertainty introduced by this error source Total counting time/mea. (s) --- 12

may limit considerably the accuracy and precision

of the analytical results if we are not attentive to it. 4. Calculate the relative standard deviation [8] as
In this section, techniques for improving and con- explained hereafter for both series of measure-
trolling the quality of the sample preparation itself ments.
will not be discussed, but only general considera- 5. If the relative standard deviation obtained in ex-
tions for evaluating the uncertainty introduced by periment 3.1 is sufficiently low, the method of
random and systematic errors due to the prepara- sample preparation is suitable. Pay special at-
tion of samples to be analyzed will be considered. tention to the results for the major constituents.
As a first precaution, since X-ray fluorescence 6. If for a particular element the obtained relative
spectrometry, like most instrumental methods of standard deviation is too high, the results of ex-
analysis, is essentially a comparative technique, it periment 3.1 can be compared with those of 3.2
is absolutely vital that both calibration reference in order to determine whether the spread is due
materials and samples to be analyzed are prepared to the sample preparation or to the instrument
in an identical and reproducible manner and pre- and counting statistics.
sented to a spectrometer that must be operated un- If required, other sample preparation methods
der the same experimental conditions. can be tested using a similar testing procedure. For
The second important precaution is to check example, for testing a new binder in the prepara-
that the repeatability of the prepared specimens is tion of pressed powder pellets, the surfacing of
sufficiently good. This means that the uncertainty metal specimens, a new flux for the preparation of
due to the sample preparation must be smaller than fused discs, etc. To do so, select another represen-
the acceptable global analytical uncertainty. It is tative homogeneous sample. Repeat the prepara-
therefore essential that even the simplest method of tion and measurement of 10 new specimens, and
sample preparation be tested for its repeatability. additionally, measure one of the prepared speci-
Only after verification that the preparation method mens 10 times. Compare both series of results as
is sufficiently reproducible should one start prepar- described hereafter. Whatever sample preparation
ing the (expensive) calibration reference materials. method you choose, always verify its repeatability
The following general procedure can be used before to begin preparing the calibration reference
to test the repeatability of the sample preparation materials.
method: As a numerical example, Table 3 compares the
1. Select a large amount of a homogeneous "pro- results of the measurement on 10 different fused
duction sample" to test. The selected sample disc specimens to 10 measurements on the same
does not have to be a calibration reference ma- fused disc.
terial. The uncertainty due only to sample preparation
2. Prepare 10 specimens from this single sample, can be calculated as follows. The total uncertainty
using the same preparation method for all 10 due to sample preparation, instrument and counting
specimens. statistics is given by the relative standard deviation
3. Prepare an analytical program to measure the of the first test:
intensities of all elements of interest. Carry out
the following two series of measurements, pref- (E % )Total = 585
⋅100 = 0.27%
213,110
erably on the same day, using the same analyti-
The uncertainty due to the instrument and counting
cal program:
statistics is given by the relative standard deviation
3.1 Measure each of the 10 specimens once.
of the second test:
3.2 Measure one of the specimens 10 times.

Vol. 18 No. 2 2001 43

 (E % )Test # 2 = 185
⋅100 = 0.09% (E % )Sample = (0.27%)2 − (0.06%)2 − 0.07%
212,996 Pr eparation

The total uncertainty of the first test is due to sam- = 0.26%

ple preparation, instrument and counting statistics which means, in this case, that the total uncertainty
and can be calculated from is mainly due to sample preparation. It is not due to
(E % )Total the errors of instrument or counting statistics,
which is what it should be! Note that in the actual
= (ε % )Counting + (E % )Instrument + (E %)Sample
2 2 2
analytical context of fused discs, the uncertainty
Statistics Pr eparation
associated with sampling is relatively low. In other
real applications (especially environmental), it is
(16) often substantially larger than any of the uncertain-
where the uncertainty due to the instrument and ties considered here.
counting statistics is given by the relative standard
deviation of the second test. Thus, we can write 7. Reporting of Analytical Results
As the conclusion to this paper, a few com-
(E % )Test #2 = (ε % )Counting
2
+ (E % )Instrument
2
(17) ments on the way of reporting analytical results are
Statistics
presented. The following example clearly shows
Combination of the last two equations leads to the problems associated with the incorrect report-
(E %)Total = (E %)Test
2
# 2 + (E % )Sample
2 ing of results. A simple numerical result, such as
Pr eparation 30.35% Cu for example, may give a wrong impres-
or sion to the reader if all analytical errors (which
include precision and accuracy) of the result are
(E %)Sample = (E %)Total
2
− (E % )Test
2
#2 not given. All these different types of information
Pr eparation
should always be supplied on the front page of any
Replacing the different uncertainties by their re- report of analyses. Otherwise, the mere fact that
spective numerical values, one gets the result (30.35% Cu) is written with two digits
(E %)Sample = (0.27%)2 − (0.09% )2 = 0.26% after the decimal point does not assure the reader
Pr eparation that such accuracy is obtainable nor does it reas-
Another way to calculate the uncertainty due to sure the reader that a subsequent measurement (re-
sample preparation is as follows. The relative peatability) will produce the same result.
counting error due to counting statistics only (es- Often, examination of the analytical results
sentially random errors) is calculated from the leads to a number of questions related to their ex-
measurements of the second test: perimental uncertainty. That is why the analysts
must absolutely employ an explicit way, and a
(ε % )Counting = 100
=
100
= 0.06% preferably accepted one, of reporting results and
Statistics I ⋅T 212,996 × 12 assessing the capabilities and limits of the analyti-
The uncertainty of the second test is due to the in- cal method. It is absolutely vital that those who use
strument and counting statistics and can be calcu- the results know exactly the limit of determination
lated from equation (17). Thus, the uncertainty due of the method (LDM), the global analytical uncer-
to the instrument only is: tainty (precision and accuracy) associated with
0.09% = (0.06% )2 + (E % )Instrument
2 each result and for which concentration range these
two parameters are valid. They must also know
or whether the given LDM parameter was derived
(E % )Instrument = (0.06% )2 + (0.09% )2 = 0.07% from only counting statistical error calculations or
from replicate determinations. Finally, the LDM is
Thus, using the equation (16), the uncertainty due more meaningful if the degree of confidence for it
to the sample preparation only is is included.
0.27% = (0.06%)2 + (0.07% )2 + (E % )2Sample The LDM of an analytical result, which is a
Pr eparation measure of the repeatability or precision, describes
Thus, the magnitude of the deviation, which occurs after

44 The Rigaku Journal

repeatedly measuring different specimens of the
Table 4. Global relative uncertainty (%) and determi-
same sample in the same analytical context. In nation limit of the method (%) over a given concentra-
other words, repeating the same measurement on tion range of analytes in rock samples analyzed by
different specimens prepared from the same sam- XRF and prepared as fused discs.
ple enables experimental estimation of the uncer- Component Calibration Estimate of Limit of
tainty of analytical results. It can be adequately range (%) global and rela- determination
tive uncertainty (%)
estimated by the absolute value, in % or ppm, of Na2O 0-10 1 0.03
the LDM (Eqn 12). It can be derived from n MgO 0-50 1 0.04
(where n=10) replicate determinations with a Al2O3 0-60 1 0.20
95.4% confidence level. This information is very SiO2 0-100 1 0.50
important since it enables to estimate the minimum P2O5 0-1 1 0.01
K2O 0-15 1 0.05
uncertainty value associated with an analytical re- CaO 0-35 1 0.01
sult. It is usually reported as a "plus-or-minus" ab- TiO2 0-3 1 0.02
solute value, in % or ppm, aside a group of results Cr2O3 0-4 1 0.01
(for example, 0.022%±0.002%). MnO 0-1 1 0.01
Fe2O3 0-90 1 0.06
The other component of analytical errors, i.e. Rb 0-0.0600 2 0.001
systematic errors, is present when a certain bias Sr 0-0.2000 10 0.002
exists in the results, as could happen if a badly de- Y 0-0.0200 10 0.001
termined calibration line is used. This bias is a Zr 0-0.2000 10 0.001
measure of the difference between the given and Nb 0-0.0400 10 0.001
Ba 0-0.3000 10 0.003
the calculated concentration value. Systematic er-
rors not only depends upon errors that arise from
the conversion of intensities into concentrations the results obtained from reference materials that
(calibration), but also from those produced by the have not participated to the calibration, to their
sample preparation, the instrument and the analyti- given (or certified) concentration values. The
cal method used for the correction of matrix ef- global relative uncertainty (in %) over a given con-
fects. centration range of a series of results for an analyte
In quantitative XRF analysis, the calibration can be estimated from
procedure, with the aid of reference materials, n 
 (C − C i calculated ) 
2

∑
i given
transforms the measured X-ray fluorescence inten-
 
sity of a particular analyte to concentration [1]. An m =1  C i given
 m
example of such a calibration line is given in Fig- (E % )global = ⋅100
ure 2. It is desirable to use several reference mate- n
rials so that the error due to calibration is held as (18)
small as possible. However, the calibration trans- where
formation is usually subject to errors depending on (E%)global Average relative analytical uncer-
the reliability of the reference materials used and tainty value in %
on the accuracy of the analytical method [12] for n Total number of calibration reference
the matrix effect corrections. If certified reference materials
materials are used, the reliability is quantifiable by m Suffix for identifying each calibration
the uncertainty that is always associated with a reference material
certified value. Although the reference materials i Element to be determined or analyte
may well be in agreement among themselves, they Ci given Given or certified concentration
nevertheless may be the cause of systematically value of element i in calibration ref-
erroneous analyses. The relative standard deviation erence materials
calculated from the regression analysis of data of Ci calculated Calculated concentration value of
the calibration line is therefore not a reliable crite- element i in calibration reference ma-
rion to estimate the global uncertainty over a given terials
range of concentrations for an analytical method.
However, the global uncertainty of the analytical The global analytical uncertainty is a combi-
results may be very well estimated by comparing nation of all sources of random and systematic er-

Vol. 18 No. 2 2001 45

 Fig. 2. Graph of the calibration line of the measured relative intensity as a function of
the calculated relative intensity for Fe in different alloys.

rors, or precision and accuracy respectively, which

Table 5. Calculation of the average relative uncertainty
from the data of the calibration line of Figure 2 for typical
can affect the final value of a result. This uncer-
alloys. Only the reference materials D807A and C1119 have tainty is usually reported as a relative value in %.
been used to calculate the slope and the intercept of the line. For major elements, the global uncertainty is usu-
Because the calibration range is very large (0-100%), only ally within 0.5 to 1%. However, it has to be kept in
results > 1% have been considered. The last two digits of mind that the given concentration values of refer-
each result are meaningless for any value > 0.10% (or 1000
ppm) ence materials are also subject to errors just as the
Reference Concentration (%) Uncertainty (%) results determined by X-ray spectrometry. Table 4
material Given Calculated Absolute Relative gives an example of the global analytical uncer-
NBS-628 0.0660 0.0855 0.0195
NBS-629 0.0170 0.0297 0.0127
tainty of the XRF analysis of rock samples pre-
NBS-644 1.3600 1.3316 -0.0284 2.08 pared as fused discs.
NBS-646 2.1400 2.1202 -0.0198 0.92 A good strategy for calculating the global rela-
D805A 97.6350 98.1277 0.4927 0.50
D807A * 97.5830 97.5949 0.0119 0.01 tive uncertainty for the type of calibration plot of
D809B 95.7560 95.9046 0.1486 0.16 Figure 2, when several reference materials are
D836 80.2450 80.8630 0.6180 0.77 available, is to use only the lowest and the highest
D837 80.9600 81.4751 0.5151 0.64
D838 78.7700 79.1955 0.4255 0.54 points of the analyte calibration range to calculate
D840 70.5500 71.5141 0.9641 1.37 the slope and the intercept of the line. The concen-
D845 83.5230 82.9450 -0.5780 0.69
D847 62.0290 61.9952 -0.0338 0.05
trations of all the other intermediary points are then
D848 85.5640 85.4016 -0.1624 0.19 calculated from this calibration line and compared
D849 84.5190 84.3856 -0.1334 0.16 to the given concentration values. As an example,
D850 71.3220 70.8900 -0.4320 0.61
C1101 0.0370 0.0374 0.0004 Table 5 gives all the data [13] necessary to calcu-
C1103 0.2600 0.2787 0.0187 late the global (or average) relative uncertainty of
C1110 0.0330 0.0361 0.0031 the calibration line of Figure 2 for typical alloys.
C1113 0.0430 0.0398 -0.0032
C1116 0.0460 0.0457 -0.0003
C1119 * 0.0300 0.0306 0.0006
8. Acknowledgments
1154 65.0600 65.2628 0.2028 0.31 Dr. P.J. Potts from The Open University and
1156 69.6700 69.7695 0.0995 0.14 Dr. S.T. Ahmedali from McGill University deserve
1159 51.0000 51.3395 0.3395 0.67
1160 14.3000 14.6420 .3420 2.39 the gratitude of the author for invaluable advice
Average: 0.68 and critical reading of the manuscript.
rors, or precision and accuracy respectively, which

46 The Rigaku Journal

 9. References [7] R. Jenkins and J. V. Gilfrich, X-Ray Spectrometry, 21,
[1] R. M. Rousseau, J. P. Willis and A. R. Duncan, X-Ray 263, (1992).
Spectrometry, 25,179, (1996). [8] R. Jenkins and J. L. De Vries, Practical X-Ray Spectrome-
[2] R. M. Rousseau and J. A. Boivin, The Rigaku Journal, 15 try, Philips Technical Library, Springer-Verlag New
(1), 13, (1998). York Inc., Second Edition, (1970).
[3] E. P. Bertin, Principles and Practice of X-Ray Spectromet- [9] N. Spielberg and M. Bradenstein, Appl. Spectrosc.,
ric Analysis, Plenum Press, New York, (1970). 17,6,(1963).
[4] International Standard, ISO 3534-1, Statistics-Vocabulary [10] R. Jenkins, An introduction to X-Ray Spectrometry, Hey-
and symbols, (1993). den & Son Ltd., (1974).
[5] P. J. Potts, A Handbook of Silicate Rock Analysis, Blackie [11] X-Ray Spectrometry Course, Sample Preparation, Philips
& Son Limited, London, (1987). Electronics Ltd., (1990).
[6] L. A. Currie, Pure and Applied Chemistry, 67, [10] 1699, [12] R. M. Rousseau, The Rigaku Journal, 18 (1), 8, (2001).
(1995). [13] R. M. Rousseau and M. Bouchard, X-Ray Spectrometry,
15, 207, (1986).

Vol. 18 No. 2 2001 47

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