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6

Quantication in XRF Analysis


of Intermediate-Thickness Samples

Andrzej A. Markowicz
Vienna, Austria
Rene E. Van Grieken
University of Antwerp, Antwerp, Belgium

I. INTRODUCTION

A number of approaches have been developed for quantitation in x-ray uorescence


(XRF) analysis of intermediate-thickness samples whose mass per unit area m fullls the
relation
mthin < m < mthick 1
where mthin and mthick are the values of mass per unit area for thin and thick samples [for
a denition, see Chapter 1, Eqs. (93) and (95)]. Intermediate samples can be preferable
to thick specimens because remaining uncertainties about mass-attenuation coecients
have a smaller eect on the analysis results, less material is required, the sensitivity
is more favorable for low-Z elements, and secondary enhancement eects are less
important.
Historically, the oldest correction method applied in quantitative XRF analysis of
intermediate-thickness samples is the emissiontransmission (ET) method in which the
specic x-ray intensities from a sample are measured successively with and without a
target positioned adjacent to the back of the sample in a xed geometry. Recently, the
ET method has thoroughly been evaluated, and both the advantages and limitations of
the technique are well identied. A number of modications of the ET method, de-
veloped in recent years, allowed an essential extension of its applicability range. To
avoid additional measurements that are inevitable in the emissiontransmission method,
some alternative correction procedures based on the use of scattered primary radiation
were also developed. In recent years, however, only a few papers have been published in
this eld.
The underlying principles as well as the ranges of applicability and the limitations of
the correction procedures applied to XRF analysis of both homogeneous and hetero-
geneous intermediate-thickness samples are outlined here.

Copyright 2002 Marcel Dekker, Inc.


II. EMISSION---TRANSMISSION METHOD

In the absence of enhancement eects and assuming monochromatic excitation, the mass
per unit area of the element i; mi , for homogeneous intermediate-thickness samples, can be
calculated from [see Eq. (90) in Chapter 1]:
Ii Ei
mi Abcorr 2
Bi
where
GI0 E0 "Ei i0 E0 !i pi 1  1=ji
Bi 3
sin 1
and Abcorr is the absorption correction factor given by
E0 csc 1 Ei csc 2 m
Abcorr 4
1  expfE0 csc 1 Ei csc 2 mg
[The symbols used in Eqs. (2)(4) are explained in Chapter 1, Eqs. (88) and (89).]
The value of the constant Bi (sometimes called the sensitivity factor) can be de-
termined either experimentally as the slope of the straight calibration line for the ith
element obtained with thin homogeneous samples or semiempirically based on both the
experimentally determined GI0 E0 value and the relevant fundamental parameters (Yap
et al., 1987; Markowicz et al., 1992a).
The absorption correction factor Abcorr represents the combined attenuation of
the primary and uorescent radiations in the whole specimen and can be determined
individually for each sample by transmission experiments (Leroux and Mahmud, 1996;
Giauque et al., 1973). These are done by measuring the x-ray intensities with and without
the specimen from a thick multielement target located at a position adjacent to the back of
the specimen, as shown in Figure 1.
If Ii S ; Ii T ; and Ii 0 are the intensities after background correction from the
sample alone, from the sample plus target, and from the target alone, respectively, then the
combined fraction of the exciting and uorescent radiations transmitted through the total
sample thickness is expressed by
Ii T  Ii S
expfE0 csc 1 Ei csc 2 mg H 5
Ii 0
After a simple transformation, Eq. (2) can be rewritten as

Figure 1 Experimental procedure used in the emissiontransmission method for the correction of
matrix absorption effects.

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Ii Ei  ln H
mi 6
Bi 1  H
The emissiontransmission method can only be applied in the quantitative XRF
analysis of homogeneous samples of which the mass per unit area is smaller than the
critical value, mcrit ; dened by
ln Hcrit
mcrit  7
E0 csc 1 Ei csc 2
where Hcrit is the critical value of the transmission factor dened by Eq. (5); in practice,
Hcrit 0:1 or 0:05:
To minimize possible absorption correction errors resulting from enhancement of
the specimen radiation by scattered target radiation, targets that yield a high ratio of
scattered to uorescent radiation should not be used.
Giauque et al. (1979) developed a modied version of the emissiontransmission
method. Using data from the attenuation measurements and Eq. (5), the values of
E0 csc 1 Ei csc 2 m T m are calculated for the energies of characteristic
x-rays of all elements present in a thick multielement target. If these values are plotted
versus the uorescence x-ray energy on a loglog scale (Fig. 2), an approximate value for

Figure 2 Curves of [m(E0) csc 1 (Ei) csc 2]m and mm(Ei) csc 2 values versus fluorescence
x-ray energy for an NBS SRM 1632 coal specimen. (From Giauque et al., 1979. Reprinted with
permission from Analytical Chemistry. Copyright American Chemical Society.)

Copyright 2002 Marcel Dekker, Inc.


E0 csc 1 can be obtained by extrapolation of the curve to the energy of the excitation
radiation. In turn, values for mEi csc 2 can be calculated, a curve for these values
drawn, and a new value for mE0 csc 1 established. This last step is iterated several
times. Using data from the latter curve, the absorption correction factors for all radiations
of interest can be calculated from Eq. (4). If some elements to be determined are major or
minor constituents, a few separate curves for mEi csc 2 values should be plotted be-
tween the preselected x-ray energies corresponding to the relevant absorption edges. In the
emissiontransmission method of Giauque et al. (1979), the incoherent scattered radiation
corrected for matrix absorption is used as the internal standard to compensate for var-
iations in sample mass, x-ray tube output, and sample geometry.
In practical applications of the emissiontransmission method, the values of the
transmission factor H [Eq. (5)] determined for a few energies of the characteristic x-rays
of some elements present in a multielement target are used to construct a curve
ln lnH1 lnT m versus ln E; which enables one to calculate the absorption cor-
rection factor Abcorr for any energy. In some cases, however, the relationship of
ln lnH1 versus ln E exhibits some discontinuities which correspond to the absorption
edges of minor (major) elements present in the unknown samples. In such cases the
approach proposed by Giauque et al. (1979), based on the construction of separate
curves for the predened energy regions, can only be used if at least two experimental
points are available for each energy region. When only one or no experimental point is
available, a modied version of the emissiontransmission method can be used (Mar-
kowicz and Haselberger, 1992). To explain the modied procedure, let us assume that a
multielement target consists of Ca, Ti, Fe, Zn, Sr, Zr, and Pb, and the material to be
analyzed contains some minor elements, such as Fe and Ca. From the ET measure-
ments, the values of A A H1 are easily obtained for higher energies (e.g., for the
characteristics x-rays of Fe, Zn, Sr, Zr, and Pb in this case) (see Fig. 3). First, a straight
line is tted to the points corresponding to Zn, Pb, Sr, and Zr (region I). Second, a
straight line of the same slope and passing through a point for Fe is constructed (region
II). If no experimental point is available for Ca, the discontinuity for the K absorption
edge of Ca has to be taken into account by applying a computation routine. In the rst
step, the product 1 WCa above  below is calculated, where WCa is the weight
fraction of Ca obtained by using a direct extrapolation of curve II and above and below
are the mass absorption coecients just above and below the K absorption edge of Ca,
respectively. Next, the corrected value of the total mass absorption coecient
cor
T ln A=m  1 csc 2 is calculated for the energy of the CaKabs edge, where A is
taken from curve II and 2 is the emerging angle for the characteristic x-rays. Based on
the cor
T value, a straight line passing through point C and having the same slope as that
one in region II is constructed (the coordinates of the point C are x ln CaKabs and
y lnln A  m1 csc 2 ). In the next step, the values of ln T m and the absorption
correction factor Abcorr are calculated for the energy of Ca characteristic x-rays based
on the straight line for region III. Because the true value of the weight fraction for Ca is
unknown, all calculations for the absorption edge of Ca (region III) are iterated until the
following convergence is obtained:

WCa n  WCa n1


 0:001 8
WCa n

where WCa n and WCa n1 are the values of the weight fractions for Ca obtained in the
subsequent iterations.
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Figure 3 Graphical explanation of the idea for the modified version of the ET method: see text for
details. (From Markowicz and Haselberger, 1992. Reprinted with permission of Pergamon Press Ltd.)

A calculation procedure applied for the Ca absorption edge can easily be repeated
for any other absorption discontinuity at a lower energy and, nally, a total absorption
curve ln ln A versus ln E is obtained.
The importance of the additional correction for the discontinuities in the absorption
properties of the samples to be analyzed was demonstrated, among others, for the analysis
of coal samples. Neglecting the absorption edges correction for Fe and Ca at the con-
centration level of around 1% resulted in considerable errors of the analysis, up to 60%
for the determination of Ca (Markowicz and Haselberger, 1992).
Van Dyck et al. (1980) developed a correction method that allows calculations of the
absorption coecients (and absorption correction factors as well) at any energy for in-
termediate-thickness samples, without additional measurements, by using the ratio of the
x-ray signals from a Zr wire positioned in front of the sample and from a Pd foil placed
behind the sample, both in a xed geometry, as shown in Figure 4. The Zr wire provides an
external reference signal ZrK; which is applied for normalization of all measured
uorescent intensities to reduce considerably the eect of variations in exciting x-ray tube
intensity and of dead-time losses.
The coecients for higher energies are calculated with an iterative program from the
experimentally measured absorption coecient at the PdL energy (2.9 keV), EPd . In the
rst step, the total attenuation coecient at the PdL energy, caused exclusively by the low-
Z elements (e.g., Z < 17) in the sample that show no characteristic peak above 3.0 keV in
the spectrum, is calculated from the normalized measured intensities, IPd T and IPd 0 and
Copyright 2002 Marcel Dekker, Inc.
Figure 4 Measurement geometry applied in an automatic absorption correction method. (From
Van Dyck et al., 1980. Reprinted by permission of John Wiley & Sons, Ltd.)

the dierent characteristic peaks recorded in the spectrum. This attenuation coecient due
to low-Z elements, low-Z EPd , is given by (Van Dyck et al., 1980)
low-Z EPd
Pn 0
lnIPd 0 =IPd T =m csc 2  E0 csc 1 =csc 2  j1 Wj j EPd
P0 9
1  nj1 Wj
where n0 is the number of characteristic peak in the XRF spectrum and j EPd is the mass
attenuation coecient for the PdL energy in the element j (McMaster et al., 1969), giving
rise to a characteristic peak in the XRF spectrum.
The weight fraction of the element j in the sample, Wj , is correlated with the recorded
characteristic peak through the sensitivity factor, routinely obtained by measuring thin
single or multielement standards. As a rst approximation, the characteristic peak in-
tensities are not corrected for absorption. In a second step, based on the low-Z EPd value,
the absorption coecients of the low-Z matrix for other energies, low-Z E, are calculated
quantitatively by assuming nearly parallel properties of the logarithmic absorption curves
ln E versus ln E.
The total mass attenuation coecient E for the characteristic x-rays of an element
in the whole sample can now be calculated, taking into account the contributions j E of
the high-Z elements:
!
Xn0 Xn0
E 1  Wj low-Z E Wj j E 10
j1 j1

The overall procedure is summarized and schematically represented in Figure 5.


Better E values [Eq. (10)] are obtained in the second and following loops by
carrying out appropriate absorption corrections to the characteristic intensities from
which the Wj values are derived using E and E0 values from the previous loop and
by including in Eq. (9) the E0 values, taken as zero in the rst loop. The iteration is
stopped when the dierence in E between two loops is negligible.
Subroutine ENHANC is applied to evaluate the enhancement eect of the PdL
x-rays caused by all elements in the sample of which the x-ray energy is higher than the
L1 ; L2 and L3 absorption edges of Pd. The intensity caused by this enhancement eect can
be considered to result in an apparent increase in IPd 0 . The enhancement contributions,
IenhPd , are added to the IPd 0 in Eq. (9). This total IPd Oeff value and the detected IPd T
signal allow us to calculate the correct  values via Eqs. (9) and (10).
A comprehensive discussion of the inuence of secondary enhancement of the PdL
x-rays by the samples as well as of the inuence of two other complicating factors, grain
Copyright 2002 Marcel Dekker, Inc.
Figure 5 The calculation steps. From the experimentally measured total absorption coefficient at
the PdL energy, m(EPd), the calculated contribution from high-Z elements (giving a characteristic
peak in the spectrum) is substracted; through this low-Z matrix contribution at the PdL energy, the
total low-Z absorption curve (dashed line) is calculated; the contribution from high-Z elements (e.g.,
Ca and Fe) is then added, to yield the total absorption curve (thick line). (From Van Dyck et al.,
1980. Reprinted by permission of John Wiley & Sons, Ltd.)

size eects, and a heterogeneous sample load is presented in the work of Van Dyck et al.
(1980). The grain size and sample heterogeneity eects induce inaccuracies on the ab-
sorption coecient determinations that may well reach 20% for particulate samples, such
as intermediate-thickness deposits of geological materials. Thus, this approach has the
same limitations as all emissiontransmission methods applied to heterogeneous samples.

A. Accuracy and Limitations of the Emission--Transmission Method


The overall (total) absolute uncertainty of the mass per unit area of the ith element, mi , can
be calculated from the law of error propagation applied to Eq. (2) (Markowicz et al., 1992b):
"      #1=2
Abcorr 2 2 Ii Ei 2 2 Ii Ei Abcorr 2 2
mi Ii Ei Abcorr Bi 11
Bi Bi B2i

where Ii Ei is the absolute uncertainty of the characteristic x-ray intensity Ii Ei (usually
provided by a computer routine applied for spectrum evaluation), Abcorr is the absolute
uncertainty of the absorption correction factor, and Bi is the absolute uncertainty of the
sensitivity (or calibration) factor Bi (usually provided by a computer calibration routine,
as a mean percent dierence between the experimental and tted values for the calibration
factors). The total relative uncertainty of the mass per unit area mi =mi is calculated from
"      #1=2
mi Ii Ei 2 Abcorr 2 Bi 2
12
mi Ii Ei Abcorr Bi

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In order to calculate Abcorr , one has to apply the law of error propagation to Eqs. (4)
and (5):
A  1  ln A
Abcorr A 12a
A  12

with A H1 [Eq. (5)] and


" #1=2
Ii 0 2 Ii T 2 Ii 0 2 Ii S 2 Ii 0 2
A 12b
Ii T  Ii S 2 Ii T  Ii S 4 Ii T  Ii S 4

where Ii 0 and Ii T are the absolute uncertainities of the characteristic x-ray
intensities obtained from the target alone and from the sample plus target, respectively.
After a simple transformation, mi =mi can be given by
"    #1=2
mi Ii Ei 2 A  1  ln A2 2 Bi 2
A 13
mi Ii Ei A  12 A2 ln A2 Bi

It is obvious that the total relative uncertainty of the weight fraction of the ith element
Wi =Wi is equal to mi =mi .
Equations (13) and (12b) can be used for calculating the total uncertainities of
the emissiontransmission method as well as the contribution from various sources of
the uncertainties Ii Ei ; Abcorr ; Bi . It has been demonstrated that in the de-
termination of trace elements, the dominant contribution to the total uncertainty is
from the uncertainty of the peak-area calculation for the characteristic x-rays of the
element of interest. In this case, the contribution from the uncertainties of the ab-
sorption correction factor and sensitivity can practically be neglected. In the determi-
nation of major elements, the largest contribution to the total uncertainty is from the
uncertainty of the absorption correction factor and=or sensitivity; in this case, the
contribution of the uncertainty of the peak-area calculation can safely be neglected.
Such a detailed analysis of the contribution of various sources of uncertainties can
be useful when there is a need to identify the most critical point of the whole
analytical procedure and some reduction of the total uncertainty of the analysis is
required.
Another factor which inuences the accuracy of the emissiontransmission
method is the heterogeneity of the sample loading. Markowicz and Abdunnabi (1991)
derived general expressions describing the accuracy of the ET method for various
types of sample loading heterogeneities (including incompletely loaded samples) within
a wide range of sample thicknesses and characteristics x-ray energies. The results,
conrmed by experiments, clearly show that inhomogeneities of sample loading may
critically aect the accuracy of the ET method, in particular in the analysis of in-
termediate-thickness samples with strong inhomogeneities and large values for the
E0 csc 1 m and Ei csc 2 m factors. The most critical inuence of sample loading
heterogeneity on the accuracy of the analytical results is observed for incompletely
loaded samples of intermediate thickness. The method proposed in the work of
Markowicz and Abdunnabi (1991) gives a possibility for evaluating the errors arising
from some types of sample loading heterogeneities as well as for evaluating the range
of applicability of the simplest version of the ET method (Markowicz et al., 1992b) if
a certain value for the total uncertainty Wi =Wi is accepted.
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III. ABSORPTION CORRECTION METHODS VIA SCATTERED PRIMARY
RADIATION

The use of scattered primary radiation in XRF analysis provides an alternative to the
common problem of matching standards of similar composition to samples to be analyzed.
The backscatter peaks are sometimes treated as uorescent peaks from internal standards
because they suer matrix absorption similar to that of uorescent peaks and behave si-
milarly with instrumental variations. They also provide the only direct spectral measure of
the total or average matrix of geological, biological, or other materials containing large
quantities of light elements, such as carbon, nitrogen, and oxygen, usually not observed by
their characteristic x-ray peaks.
X-ray uorescence matrix correction methods based on the use of scattered radiation
have mostly been applied in quantitative analysis of innitely thick samples under a wide
variety of experimental conditions, including discrete and continuum primary radiation
sources and detection by both wavelength- and energy-dispersive systems (Andermann
and Kemp, 1958; Kalman and Heller, 1962; Taylor and Andermann, 1971, 1973; Leo-
nardo and Saitta, 1977; Livingstone, 1982; Kikkert, 1983; Markowicz, 1984). The scat-
tered-radiation methods utilize the incoherent (Compton) and=or coherent (Rayleigh)
scatter peaks from line excitation sources or the intense high-energy region from con-
tinuum sources.

A. Absorption Corrections Based on Incoherent Scattered Radiation


For specimens of less than innite thickness, the intensity ICom of Compton-scattered
radiation can be expressed by (Meier and Unger, 1976)

k0 I0 Com E0 1  expfE0 csc 1 ECom csc 2 mg


ICom 14
E0 csc 1 ECom csc 2

where k0 is a constant for a given measurement geometry and detection eciency, Com E0
is the Compton mass-scattering coecient of the sample material for the primary radiation
of energy E0 cm2 =g; ECom is the total mass-attenuation coecient of the sample
material for Compton-scattered primary radiation of energy ECom cm2 =g [see Eq. (52) in
Chapter 1]. Equation (14) is valid for monochromatic excitation.
Assuming that the relation of the atomic number to the mass number is constant for
every element to be found in the sample and that E0 ECom , the following sim-
plied formula for the intensity of Compton-scattered radiation from a multielement
sample can be obtained:

k01 I0 f1  expE0 csc 1 1 csc 2 =csc 1 m g


ICom 15
E0 csc 1 1 csc 2 =csc 1
where k01 is a constant for given geometry of measurement and the energy of the incident
radiation. The value of the product k01 I0 is determined experimentally from a reference
scatterer and is valid as long as the reference scatterer has a matrix that is not too dierent
from that of the specimens.
Kieser and Mulligan (1979) worked out a method based on the use of the incoherent
scatter radiation, which gives accurate mass absorption coecients for a limited average Z
range. The mass absorption coecient E0 for specimens of intermediate thickness is
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found from Eq. (15) after a numerical solution. To obtain a value of the mass absorption
coecient E at any energy E, Kieser and Mulligan (1979) assumed that the slope of the
curve log E versus log E is constant for all elements (approximately 2.7) over a range
of x-ray energies. The proposed Compton-scattered method for the determination of an
intermediate specimens mass absorption coecient at any energy can be applied as long
as no absorption edge of a major or minor element intervenes. When the values of the E
are determined, calculation of the absorption correction factor [Eq. (4)] is straightforward
if, of course, the mass of the sample to be analyzed is known.
A modied uorescent Compton correction method for quantitative XRF of in-
termediate specimens was developed by Holynska and Markowicz (1979). The method is
based on the use of the measured x-ray uorescent intensities of all determined elements
and the intensity of Compton-backscattered radiation. The authors derived the following
expression for the determination of the mass per unit area of the element i, mi:
ai I i
mi Pn0 16
1 l1 ail Il bi ICom =m

where ai ; ail ; and bi are constant coecients obtained experimentally on the basis of
standard samples and n0 is the number of the elements to be determined, including the ith
element. As is seen from Eq. (16), the absorption matrix correction is carried out via the
intensities of characteristic x-rays of all elements determined and the intensity ICom, re-
ecting, for the most part, the variations in the composition of light matrix. To apply the
absorption matrix correction, Eq. (16), the total mass per unit area of the specimen must
be evaluated, for example, by sample weighing. This uorescentCompton correction
method can be used in the XRF analysis of homogeneous intermediate-thickness samples
in a limited range of mass per unit area (m < 10mthin).

B. Absorption Corrections Based on Both Coherent and Incoherent


Scattered Radiations
Several absorption correction methods based on both coherent and incoherent scattered
radiations have been developed, mostly in the 1970s and 1980s, and applied in quantitative
XRF analysis of intermediate samples. This group of correction methods is represented
either by relatively simple approaches (Bazan and Bonner, 1976; Markowicz, 1979) or by
very sophisticated fundamental parameter procedures (Nielson, 1977; Van Dyck and Van
Grieken, 1980; Nielson et al., 1982; Nielson and Rogers, 1984) providing superior ana-
lytical exibility.
For specimens of less than innite thickness, the intensity Icoh of coherent scattered
radiation can be calculated from

k00 I0 coh E0
Icoh f1  expE0 csc 1 csc 2 m g 17
E0 csc 1 csc 2

where k00 is a constant for a given measurement geometry and detection eciency for the
primary x-rays of energy E0 , and coh E0 is coherent mass-scattering coecient of the
sample material for the primary radiation (cm2=g) [see Eq. (73) in Chapter 1].
Bazan and Bonner (1976) showed, for the rst time, a linear relation between the
eective absorption coecient (dened as the sum of the sample absorption coecients for
exciting and characteristic x-rays) and the ratio of incoherent to coherent scattering.
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However, the coecients of the calibration line varied somewhat with the matrix, and this
hampered practical applications of this simple approach.
Markowicz (1979) found that, theoretically the sensitivity of the absorption cor-
rection via the incoherent=coherent scattered x-ray intensities ratio is better than that of
the absorption procedure involving each of the scattered radiations individually. For in-
termediate-thickness samples, in a limited range of rather small values of mass per unit
area, the intensities of the Compton-scattered radiation ICom and the coherent scattered
radiation Icoh are dierent functions of the total mass-attenuation coecient of the
incident radiation E0 ; the intensity ICom is a linearly decreasing function and the
intensity Icoh appears to be a linearly increasing function of the E0 . For a limited
range of E0 values, the following simple expression can be used to evaluate E0
(Markowicz, 1979):

E0 C1 C2 m C3 r C4 mr 18
where
ICom
r
Icoh
and C1C4 are constants calculated by the least-squares t on the basis of experimental
results for standard samples.
The values of the total mass-attenuation coecient of the uorescent radiation in a
whole sample, Ei , is obtained from the simple dependence of the Ei =E0 ratio on
the values E0 , calculated separately for each element to be determined. Finally, sample
weighing provides the value of mass per unit area, m, and the calculation of the absorption
correction factor Abcorr via Eq. (4) can be simply performed if, of course, the values of the
eective angles 1 and 2 are evaluated experimentally or theoretically. The applicability
of the proposed matrix correction method (Markowicz, 1979) involving both incoherent
and coherent scattered primary radiations is limited to XRF analysis of intermediate-
thickness samples of mass per unit area smaller than about 10mthin.
A backscattered fundamental parameters (BFP) method for quantitative XRF
analysis of intermediate samples of variable composition and thickness was developed by
Nielson (1977). The method utilizes thin-lm multielement calibration of the spectrometer
and mathematical matrix correction in which the samples are modeled as a composite of
heavy elements, which are quantied through their characteristic radiation, and light
elements, estimated through the coherent and incoherent x-ray scatter peaks. Figure 6
schematically illustrates the basis for analyzing the heavy elements (Z > 13) and the light
elements (H, C, N, O, Na, and others), which must be estimated by the dierence from the
scattered x-ray peaks. The BFP method utilizes coherently and incoherently scattered
x-rays to identify and estimate the quantities of two light elements representative of the
light-element portion of sample matrix. The quantities of the two light elements a and b
are estimated by solving for Wa and Wb in the simultaneous equations
X
n0
gIcoh  Wj cohj E0 Wa coha E0 Wb cohb E0 19
j1

and
X
n0
hICom  Wj Comj E0 Wa Coma E0 Wb Comb E0 20
j1

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Figure 6 Light-element contributions to x-ray scattering, from which absorption corrections are
computed. (From Nielson, 1977. Reprinted with permission from Analytical Chemistry. Copyright
American Chemical Society.)

where g and h are the geometry-dependent calibration factors determined experimentally


by using any standard of known total composition. Because several light-element pairs
may satisfy Eqs. (19) and (20), the pair is chosen whose incoherent=coherent scattering
cross-sectional ratios lie immediately on either side of the ratio of the observed scatter
attributable to light elements (Nielson, 1977):
Pn 0
Coma E0 hICom  j1 Wj Comj E0 Comb E0
< P0 < 21
coha E0 gIcoh  nj1 Wj cohj E0 cohb E0

The heavy- and light-element concentrations are used in computing the absorption
correction factor Abcorr [Eq. (4)] and the enhancement correction factor [Eq. (91) in
Chapter 1]. Because the concentrations and corrections are interdependent, all calculations
are carried out by iteration [for more details see (Nielson, 1977)].
To improve the sensitivity of the determination of low-Z elements, Sanders et al.
(1983) extended the previously described BFP method. The new method utilizes the co-
herent and incoherent backscatter intensities to compute matrix corrections (Nielson and
Sanders, 1982) from the combined results of two separate energy-dispersive XRF
(EDXRF) data from dierent (TiK and ZrK) excitation sources. The Ti-excited spec-
trum allows a more sensitive determination of elements in the AlCa range.
The coherent=incoherent scatter ratio is also applied in an absorption correction
procedure developed by Van Dyck and Van Grieken (1980) for monochromatic x-ray
excitation. In this method, coherent and incoherent scattered radiations are used to cal-
culate, rst, the eective mass of the sample and, second, the absorption coecients for
x-rays of interest and, hence, the absorption correction factors. The eective thickness is
the sample thickness weighted at every point for the excitation-detection eciency, in the
same way as the measured characteristic radiation is weighted.
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Assuming that the major elements of the sample do not dier too greatly in atomic
number, the eective thickness me can be calculated from (Van Espen et al., 1979)

ICom
meff 22
fb0 Abcorr ECom b0 Icoh Abcorr ECom =a0 ICom Abcorr Ecoh b1 ga1  b1 1

where a0 ; a1 ; b0 ; and b1 are experimental constants obtained by tting the results of


measured standards; for mixtures or compounds, the coherent and incoherent scatter
factors Scoh and SCom , (in fact, the relevant mass-scattering coecients), are given by

X
n
Scoh a0 Wj Zaj 1
j1

and
X
n
SCom b0 Wj Zbj 1 23
j1

respectively. Abcorr(ECom ) and Abcorr(Ecoh ) are the absorption correction factors for the
incoherent and coherent scatter radiation, respectively, as dened in Eq. (4).
A reasonably accurate eective mass is obtained by modeling the sample as a
composite of high-Z elements, calculated from their characteristics peaks using Eq. (2),
and of a light matrix with mass per unit area, mlow-Z , evaluated from the coherent and
incoherent scatter peaks after subtraction of the high-Z element contribution. The method
for the determination of the eective thickness allows the analysis of samples of hetero-
geneous thickness and irregular shape.
More recently, Araujo et al. (1990) have developed a very similar procedure for
eective sample mass assessment of intermediate thickness samples via the coherently and
incoherently scattered radiation, as a rst step in the automated matrix eect evaluation,
for the case of ltered polychromatic continuum excitation with a Rh tube. Validation
with geological standards and deposited slurries on Mylar foils and Nuclepore lters gave
very satisfactory results.
In the method proposed by Van Dyck and Van Grieken (1980), calculation of the
mass-attenuation coecient for x-rays of interest is preceded by an evaluation of the
mass-attenuation coecient m (2.956 keV) at the ArKa energy (2.956 keV). This energy is
preferred because it is at the lower end of the energy range that can safely be used in
conventional EDXRF analysis and because, when working under vacuum, it is situated
in a peak-free part of an XRF spectrum. The value of m (2.956 keV) is derived from the
ratio coherent to incoherent scatter intensities R, based on the relationship (see Fig. 7)
of the calculated mass-attenuation coecient at 2.956 keV versus the measured R ratio:

2:956 keV g0 g1 R g2 R2 24

where g0 ; g1 ; and g2 are constant coecients derived by means of a least-squares t based


on the experimental results with standard samples. To improve the accuracy of the
method, the mass absorption coecient of the low-Z matrix at 2.956 keV, mlow-Z
(2.956 keV), must be calculated from the measured ratio of coherent to incoherent scatter
intensities, corrected for the high-Z elements contribution using their characteristic x-ray
intensities. Through this low-Z matrix contribution at 2.956 keV, the total low-Z ab-
sorption curve is calculated (in full analogy to the low-Z matrix contribution at the PdL
Copyright 2002 Marcel Dekker, Inc.
Figure 7 Calculated mass absorption coefficient at 2.956 keV versus measured coherent=incoher-
ent scattered intensity ratios for pure elements and compounds (circles) and a graphitesulfur
mixture (crosses). (From Van Dyck and Van Grieken, 1980. Reprinted with permission from
Analytical Chemistry. Copyright American Chemical Society.)

energy in Fig. 5). Finally, the mass absorption coecients for the dierent x-ray energies E
are calculated by adding the low-Z and high-Z absorption contributions [see the total
absorption cure, Eq. (10) and Fig. 5].
The proposed procedure for the automatic determination of the mass-attenuation
coecient, based on the coherent=incoherent scatter ratio, has several obvious merits
compared with the emissiontransmission absorption correction method. First, there is
no supplementary measurement or work needed [apart from experimentally obtaining
the semiempirical dependence of the  (2.956 keV) on the R ratio (Fig. 7) and sensi-
tivity factors Bi , Eq. (2), on the basis of thin standard samples], because the additional
information on a sample composition is present in the spectrum itself. Second, because
the energies of coherently and incoherently scattered primary radiation, from which the
information is extracted, are higher than that of the incident radiation used in trans-
mission experiments, secondary eects (i.e., grain size eects, inhomogeneous thickness
of the sample, and irregular sample surface) are less important. A third positive point
Copyright 2002 Marcel Dekker, Inc.
of the described procedure (Van Dyck and Van Grieken, 1980) is the independence,
within certain limits, of the analytical results on the mass of the specimen. Also, it is
worth emphasizing the capability of determining reasonably accurate mass absorption
coecients when the mean atomic number of the sample varies drastically.
Most of the existing correction procedures in XRF analysis of intermediate-thickness
samples ignore the enhancement eect. It appears, however, that for some special cases,
the enhancement eect should be taken into account. Van Dyck et al. (1986) derived
theoretical formulas for secondary uorescent x-ray intensities in medium-thickness
samples based on the Sherman equations. Their computer routine for enhancement cor-
rections was incorporated into an overall program for evaluation of x-ray spectra and
calculation of x-ray absorption correction factors from scatter peaks.
The methods, based on coherent and incoherent scatter radiation, developed by
Van Dyck and Van Grieken (1980) for overall matrix eect corrections in the case of
monochromatic excitation and by Araujo et al. (1990) for eective sample mass
determination in case of polychromatic radiation have later been expanded by He and
Van Espen (1991) into a general and versatile procedure for quantitative EDXRF with
polychromatic excitation. The comprehensive method uses the scattered radiation to es-
timate the composition and mass of the low-Z element matrix (with optimal use of the
fundamental parameter approach) and also uses the characteristic x-ray peaks to estimate
the concentrations of the higher-Z elements. An iterative process is then executed. Using
the initially estimated sample mass and composition, the weight fraction of each element is
calculated until the calculated composition converges. The absorption and enhancement
corrections are calculated from the latest iteration. Better sample mass, low-Z matrix
composition, and analyte concentrations are computed after this. This overall procedure is
repeated again until subsequent overall iterations do not yield signicant dierences. The
method is, in principle, applicable to samples of any thickness and composition and to
polychromatic excitation. The procedure has been implemented as part of the popular
software package AXIL-QXAS (Van Espen et al., 1997), which includes spectrum ac-
quisition and spectrum analysis and runs on a PC. Excellent quantitative results have been
obtained with it.
Wegrzynek et al. (1993) have recently developed a direct correction procedure for the
enhancement eect in intermediate thickness samples, which is based on the results of the
emissiontransmission measurements and does not require any iterative calculations. The
enhancement term ENHi is calculated for the intermediate-thickness samples from
(Wegrzynek et al., 1993)

1
ENHi D 1SUM1 DSUM2 SUM3 25
2i E0

with

  1
E0 Ei
D exp m 1 25a
sin 1 sin 2

X

sin 1 E0 =Eq
SUM1 i Eq Kjq E0 Wj ln 1
j;q
E0 sin 1

sin 2 Ei =Eq
ln 1 25b
Ei sin 2

Copyright 2002 Marcel Dekker, Inc.



X

sin 1 E0 =Eq
SUM2 i Eq Kjq E0 Wj ln  1
j;q
E0 sin 1

sin 2 Ei =Eq
ln  1 25c
Ei sin 2
(
X
SUM3 i Eq Kjq E0 Wj
j;q
 
 
sin 1 sin 2 E0 m
 exp
E0 Ei sin 1
 
 
Ei m   E0 Ei
exp Ei Eq m exp m
sin 2 sin 1 sin 2

 
  
sin 1 E0 sin 2 Ei
 Ei  Eq m Ei  Eq m
E0 sin 1 Ei sin 2

 
  
sin 1 E0 sin 2 Ei
 Ei  Eq  m  Ei  Eq  m
E0 sin 1 Ei sin 2
25d
Zx X
1 n
expt dt x
Eix  ln jxj  Exponential integral
t n1
n  n!
1
 0:577215664 . . .  Euler constant
where
i Eq is the photoelectric mass absorption coecient for the ith element at the
energy of the qth characteristic line of the jth enhancing element (Eq ),
Eq is the total mass absorption coecient for the sample at the energy Eq ,
!
1
Kjq E0 j E0 1  j !j pqj
Jq
Jqj and pqj are the jump ratio for the relevant absorption edge and probability of the
emission of the qth characteristic x-ray of the jth element, respectively.
The calculation of the enhancement eect correction is included in a complete pro-
cedure based on the emissiontransmission measurements (Holynska et al., 1994). In the
rst step, the calibration of the XRF system is performed [to nd the values of GI0 E0 "Ei ],
and sin 1 and sin 2 are determined from the x-ray measurements for single-element
standard samples of known mass per unit area. In the next step, the concentrations of the
elements not enhanced by any other element present in the sample are calculated (with the
absorption eect correction based on the emissiontransmission measurements). In the nal
step, the correction for the enhancement eect is made; the values of the fundamental
parameters are taken from the published tables, whereas the values of E0 ; Ei , and
Eq are derived from the results of the emissiontransmission measurements.
The enhancement factor for the intermediate thickness samples, ENHi, can also be
assessed by using another simple formula (Markowicz et al., 1992b; Austrian Matrix
Correction Routine, 1990):
X
ENHi ENHi thick Wj 1  expfEj mg 26
j

Copyright 2002 Marcel Dekker, Inc.


with (ENHi)thick is the enhancement factor for the thick sample of the same composition as
the intermediate thickness sample to be analyzed:
 
1 1 j E0
ENHi thick 1 !j p j i Ej
2 Jj i E0
  
E0 = sin 1
 ln 1 sin 1 E0 1
Ej
  
Ei = sin 2
ln 1 sin 2 Ei 1 26a
Ej

where pj is the transition probability for a given spectral line in an x-ray series of the
enhancing jth element. Also in this case, the emissiontransmission measurements can be
used to support the enhancement eect correction. The enhancement factor is calculated
either for each spectral line of the enhancing element separately or for a weighted average
energy of the whole x-ray series. The dierences in the results obtained by using the two
approaches are practically negligible (Markowicz et al., 1992b). Equation (26), although
very simple, can also be applied in order to (1) dene the region of sample thickness where
the enhancement eect is negligible (or smaller than a certain predened level) and (2) to
determine the minimum sample thickness for which the bulk enhancement correction can
already be used.

IV. QUANTITATION FOR INTERMEDIATE-THICKNESS GRANULAR SPECIMENS

The fundamentals of the quantitative XRF analysis of granular specimens involve typical
problems of radiation physics (i.e., the interaction of photons with a specimen of nite
size).

A. Particle Size Effects in XRF Analysis of Thin and Intermediate-Thickness


Specimens
The analysis of granular materials by XRF, when traditional methods of fusing or
grinding cannot be used, requires careful consideration of the so-called particle size eects.
These eects exist in XRF analysis of any granular materials, irrespective of the mass per
unit area of the specimen, and may constitute a major source of error in quantitative
analysis. The size of particles aects not only the intensity of characteristics x-rays but the
intensity of both backscattered and transmitted x-rays and low-energy g-radiation as well
(Van Dyck et al., 1980; Berry et al., 1969).
Dierent models have been proposed to account for the inuence of particle size on
the characteristic x-ray intensity leaving the sample (Berry et al., 1969; Claisse and
Samson, 1962; Lubecki et al., 1968; Hunter and Rhodes, 1972; Rhodes and Hunter, 1972;
Hawthorne and Gardner, 1978; Krasnopolskaya and Volkov, 1986). Many of these
models involve relatively complex calculations, particularly when the particle size eects
for thick granular samples must be evaluated. This section is limited to the particle size
eects in the quantitative XRF analysis of thin and intermediate-thickness (monolayer)
samples.
For granular intermediate-thickness samples, the mass per unit area of the element,
i; mi , is given by (Rhodes and Hunter, 1972)
Copyright 2002 Marcel Dekker, Inc.
Ii Ei
mi 27
Bi Fi
where Bi is the sensitivity factor as in Eq. (1) and Fi is the heterogeneity factor which for a
certain discrete particle size is dened by
1  expf E0 csc 
1 f Ei csc 2 ar
Fi 28
f E0 csc 1 f Ei csc 2 ar

where f E0 and f Ei are the linear attenuation coecients (cm1) for primary and
uorescent radiation in uorescent particles, respectively, and ar is the radiometric particle
diameter.
The radiometric diameter, introduced by Claisse and Samson (1962), represents the
mean geometrical path of x-rays through one particle. These and many other authors (Berry
et al., 1969; Lubecki et al., 1968; Hunter and Rhodes, 1972; Rhodes and Hunter, 1972) have
taken ar as simply equal to the volume of the grain divided by the particle area presented to
the radiation, averaged over all possible orientations of the grain. Hence, for spherical
particles, the radiometric diameter is equal to 0.67a (with a geometric diameter). One can
easily visualize, however, that such an approach assumes equal weighting of the con-
tribution from all possible radiative paths to the average. In view of the dierent absorption
eects themselves, this is untrue. Markowicz et al. (1980) introduced, instead of the com-
monly used radiometric diameter approach, the concept of an eective absorption-weighted
radiometric diameter for uorescent radiation, depending on both the geometry and ab-
sorption eects, and provided a comparison of these two approaches for single spherical
particles for two excitation-detection geometries ( and /2). This alternative approach
allows quantitative evaluation of the discrepancies resulting from the concept ar particle
volume=average area. It was concluded that for the  geometry, both approaches give
practically the same results (maximum relative dierences amount only to 5%), but for /2
geometry, the radiometric diameter approach can safely be applied only for very small
particles and=or at relatively high energies of primary radiation (Markowicz et al., 1980).
For samples with a certain particle size distribution described by a function far , the
heterogeneity factor Fi can be calculated according to the formula (Rhodes and Hunter,
1972)
aZr max
far 1  expar f E0 csc 1 f Ei csc 2 dar
Fi 29
f E0 csc 1 f Ei csc 2 ar
ar min

where ar min and ar max are the smallest and the largest radiometric particle diameters,
respectively, and
dVf
far 30
Vf t dar
where dVf is the volume of uorescent particles having a size between ar and ar dar and
Vf t is the total volume of the uorescent particles.
The theoretical predictions given by Eqs. (28) and (29) have been compared with the
experimental results for the heterogeneity factors obtained for samples with some discrete
particle sizes and various particle size distributions (Holynska and Markowicz, 1981). For
granular samples of copper sulde, a satisfactory agreement has been obtained; for samples
of iron oxide, some discrepancies due to agglomeration of the particles have been observed.
Copyright 2002 Marcel Dekker, Inc.
An in-depth study of the inuence of sample thickness, excitation energy, and
excitation-detection geometry on the particle size eects in XRF analysis of intermediate-
thickness samples was carried out and the results are presented in the work of Van Dyck
et al. (1985).

B. Correction Methods for the Particle Size Effect in XRF Analysis


of Intermediate-Thickness Specimens
As already mentioned, the heterogeneity factor Fi describing the magnitude of the particle
size eect in XRF analysis of thin and monolayer samples can simply be calculated if the
particle size or the function of the particle size distribution is known. This occurs in XRF
analysis of air particulates (or aerosols), for example, when special sampling techniques,
involving a cascade impactor, are applied. At dierent stages of the cascade impactor, the
particles of denite sizes are collected (Katz, 1977) and calculation of the heterogeneity
factor Fi may be straightforward if, of course, the kind of uorescent particles is known.
A simple empirical particle size correction factor 1 ba2 was proposed by Criss
(1976), in which a is the particle diameter b is a coecient that depends on particle
composition and experimental conditions. The author has provided a table of the values
for b for the determination of 48 dierent elements in 200 compounds using either a Cr- or
W-target x-ray tube.
Another correction for the particle size eect based on the model of Berry et al.
(1969), also requiring evaluation of the particle size in a sample, is due to Nielson (1977).
All the particle size corrections mentioned are of limited applicability because eva-
luation of a particle size or particle size distribution function must be done before XRF
analysis. Moreover, in many cases it may be necessary to consider how the indirectly
determined particle sizes relate to true sizes. However, even when there is some uncertainty
in the sizes and compositions of the particles, which are input parameters in the particle
size correction, it is better to make an appropriate correction than no correction at all.

1. Empirical Particle Size Correction Method Using Dual Measurements


To overcome the problems encountered when calculated particle size correction factors are
applied in the quantitative XRF analysis of granular samples, a particle size correction
method based on dual measurements of characteristic x-rays excited by x- or g-radiation of
two dierent energies was developed (Holynska and Markowicz, 1982). The method utilizes
the dierence in the particle size eect for two excitation energies and oers the possibility
of experimental detection and correction of this eect. In general, these two excitation
energies should be chosen so that the eect of particle size is small for one of them and large
for the other. Thus, the measured intensities of the characteristic x-rays of the element to be
determined are dierent functions of the particle size. The ratio of these two intensities
is sensitive to the particle size and it can be used for obtaining the particle size correction
factor Ki 1=Fi . First, a calibration curve giving the relationship between the correction
factor Ki2 and the ratio Ii1 =Ii2 rel must be plotted. The ratio Ii1 =Ii2 rel is given by
 
Ii1 Ii1 =Ii2
31
Ii2 rel Ii1 =Ii2 hom
where Ii1 =Ii2 is the ratio of the intensities of the characteristic x-rays of the ith element
excited in a granular sample by primary x-rays of two dierent energies (indexes 1 and 2,
respectively) and Ii1 =Ii2 hom is the same for a thin homogeneous sample. Taking into
Copyright 2002 Marcel Dekker, Inc.
account that in the thin-sample technique, interelement eects may be neglected, single-
element standard samples can be used to obtain the Ii1 =Ii2 hom ratio. The calibration curve
mentioned earlier can be obtained either theoretically or experimentally with the use of
calibration samples of known discrete particle size fractions. It has been shown (Holynska
and Markowicz, 1982) that there is also a possibility of applying such a calibration curve
for granular samples with various particle size distribution functions. For a p geometry,
the calibration curves for the determination of the correction factor Ki2 are described by
the equation (Markowicz, 1983)
 
Ii1 t0 ar
Ki2 32
Ii2 rel 1  et0 ar
where
f E01 f Ei
t0 33
f E02 f Ei
34
 f E02 f Ei
f E01 and f E02 are the linear absorption coecients for primary radiation of two
dierent energies (indexes 1 and 2, respectively) in uorescent particles (cm1). The par-
ticle size correction factor Ki2 is given by
ar
Ki2 35
1  ear
The proposed method of particle size correction was veried experimentally for the
determination of copper, applying 238Pu and 241Am radioisotopes as sources of primary
radiation, and a satisfactory agreement between theoretical predictions and experimental
results was reported (Holynska and Markowicz, 1982).

2. Applicability of the Particle Size Correction Method


Accurate determination of the correction factor Ki2 is mainly aected by uctuations
resulting from counting statistics in all measured intensities of the characteristic radiation.
The absolute error Ki2 in determining the correction factor Ki2 can be calculated from
the formula
t0 ar
Ki2 Sc 36
1  et0 ar
where Sc is standard deviation resulting from counting statistics for the ratio Ii1 =Ii2 rel .
The relative error in determining the particle size correction factor Ki2 is given by
Ki2 Sc
Sr 37
Ki2 Ii1 =Ii2 rel
where Sr is relative standard deviation resulting from counting statistics for the ratio
Ii1 =Ii2 rel .
Equations (32) and (37) enable us to estimate the applicability of the particle size
correction method. This can be done with the aid of Figure 8. From two families of curves
in Figure 8, one can estimate the maximum value of the particle size correction factor
Ki2 max that can be determined with the particle size correction method for given values of
Sr and t0 . Figure 9 presents the theoretical relationship of the maximum value of the
correction factor Ki2 max with the parameter t0 for dierent values of the relative standard
Copyright 2002 Marcel Dekker, Inc.
Figure 8 Theoretical relationship of the particle size correction factor Ki2 with the ratio of the
intensities Ii1 =Ii2 rel for different values of the parameter t0 (family curves) and with the error Ki2
for different values of the relative standard deviation Sr (family of straight lines). (From Markowicz,
1983. Reprinted by permission of John Wiley & Sons, Ltd.)

deviation Sr ; Figure 10 shows the theoretical relationship of Ki2 max with Sr for dierent
values of t0 . The families of curves shown in Figures 9 and 10 allow us to determine the
application limits of the particle size correction method [i.e., to determine Ki2 max in
various congurations]. In practice, however, it is more interesting to know the maximum
value of the radiometric particle diameter for which the particle size eect can still be
corrected. This can be determined from Eq. (32).

3. Selection of the Optimum Measurement Conditions


When the ith element is present in a given chemical compound and the maximum values of
the radiometric diameter of the particle in a sample are known, it is possible to dene the
optimum value t0opt of the parameter t0 for a given energy of exciting radiation E02 .
Copyright 2002 Marcel Dekker, Inc.
Figure 9 Theoretical relationship of the maximum value of the particle size correction factor
Ki2 max with the parameter t0 for different values of the relative standard deviation Sr : topt
0
is the
0
optimum value parameter t (see text for details). (From Markowicz, 1983. Reprinted by permission
of John Wiley & Sons, Ltd.)

The value of t0opt can be determined from Figure 9 for a given value of the relative standard
deviation Sr . Thus, one can obtain the following inequality, which should be fullled by
the parameter t0 :
t0  t0opt 38
This means that the value of the energy of the exciting radiation E01 of the correction
source should fulll the inequality
E01
E01 opt 39
where E01 opt is the energy of the exciting radiation E01 for which t0 t0opt . Taking into
account that the eciency of photoexcitation depends on the energy of the primary
Copyright 2002 Marcel Dekker, Inc.
Figure 10 Theoretical relationship of the maximum value of the particle size correction factor
Ki2 max with the relative standard deviation Sr for different values of the parameter t0 : Sr 0 is the
maximum acceptable value of the relative standard deviation Sr (see text for details). (From
Markowicz, 1983. Reprinted by permission of John Wiley & Sons, Ltd.)

radiation, the practical conclusion can be drawn that the values of both the parameter t0
and the energy of the exciting radiation E01 should be as close as possible to the values of
t0opt and E01 opt , respectively.
On the other hand, for a given pair of sources of primary radiation (i.e., for a given
value of the parameter t0 ), it is possible to estimate, using Figure 10, the maximum ac-
ceptable value Sr 0 of the relative standard deviation of the ratio Ii1 =Ii2 rel . In con-
sequence, the appropriate measurement times and=or activities of the sources of primary
radiation can be selected.
Although the correction method may look complicated, it is currently the only
real correction procedure dealing with the particle size eect in XRF analysis of granular
intermediate-thickness specimens. The idea of applying dierent excitation x-ray energies to
estimate particle size corrections was also exploited by Nielson and Rogers (1986).
Copyright 2002 Marcel Dekker, Inc.
REFERENCES

Andermann G, Kemp JW. Anal Chem 30:1306, 1958.


Araujo MF, Van Espen P, Van Grieken R. X-ray Specrom 19:29, 1990.
Austrian Matrix Correction Routine, Description of the Program, Technical University of Graz,
Austria, 1990.
Bazan F, Bonner NA. Adv X-ray Anal 19:381, 1976.
Berry PF, Furuta T, Rhodes JR. Adv X-ray Anal 12:612, 1969.
Claisse F, Samson C. Adv X-ray Anal 5:335, 1962.
Criss JW. Anal Chem 48:179, 1976.
Giauque RD, Garrett RB, Goda LY. Anal Chem 51:511, 1979.
Giauque RD, Goulding FS, Jaklevic JM, Pehl RH. Anal Chem 45:671, 1973.
Hawthorne AR, Gardner RP. X-ray Spectrom 7:198, 1978.
He F, Van Espen PJ. Anal Chem 63:2237, 1991.
Holynska B, Markowicz A. X-ray Spectrom 8:2, 1979.
Holynska B, Markowicz A. X-ray Spectrom 10:61, 1981.
Holynska B, Markowicz A. X-ray Spectrom 11:117, 1982.
Holynska B, Ptasinski J, Wegrzynek D. Appl Radiat Isot 45:409, 1994.
Hunter CB, Rhodes JR. X-ray Spectrom 1:107, 1972.
Kalman ZH, Heller L. Anal Chem 34:946, 1962.
Katz M (ed), Methods of Air Sampling and Analysis. Washington, DC: American Public Health
Association, 1977, p 592.
Kieser R, Mulligan TJ. X-ray Spectrom 8:164, 1979.
Kikkert J. Adv X-ray Anal 26:401, 1983.
Krasnopolskaya NN, Volkov VF. X-ray Spectrom 15:3, 1986.
Leonardo L, Saitta M. X-ray Spectrom 6:181, 1977.
Leroux J, Mahmud M. Anal Chem 38:76, 1966.
Livingstone LG. X-ray Spectrom 11:89, 1982.
Lubecki A, Holynska B, Wasilewska M. Spectrochim Acta B23:465, 1968.
Markowicz A. X-ray Spectrom 8:14, 1979.
Markowicz A. X-ray Spectrom 12:134, 1983.
Markowicz A. X-ray Spectrom 13:166, 1984.
Markowicz A, Abdunnabi AA. X-ray Spectrom 20:97, 1991.
Markowicz A, Haselberger N. Appl Radiat Isot 43:777, 1992.
Markowicz A, Haselberger N, Mulenga P. X-ray Spectrom 21:271, 1992a.
Markowicz A, Van Dyck P, Van Grieken R. X-ray Spectrom 9:52, 1980.
Markowicz A, Haselberger N, El Hassam HS, Sewando MSA. J Radioanal Nucl Chem 158:409,
1992b.
McMaster WH, Delgrande M, Mallett JH, Hubbell JM. University of California. Lawrence
Radiation Laboratory Report, UCPL-50174, 1969.
Meier H, Unger E. J Radioanal Chem 32:413, 1976.
Nielson KK. Anal Chem 49:641, 1977.
Nielson KK, Rogers VC. Adv X-ray Anal 27:449, 1984.
Nielson KK, Rogers VC. Adv X-ray Anal 29:587, 1986.
Nielson KK, Sanders RW. The SAP3 Computer Program for Quantitative Multielement Analysis by
Energy-Dispersive X-ray Fluorescence, US DOE Report PNL-4173, 1982.
Nielson KK, Sanders RW, Evans JC. Anal Chem 54:1782, 1982.
Rhodes JR, Hunter CB. X-ray Spectrom 1:113, 1972.
Sanders RW, Olsen KB, Weiner WC, Nielson KK. Anal Chem 55:1911, 1983.
Taylor DL, Andermann G. Anal Chem 43:712, 1971.
Taylor DL, Andermann G. Appl Spectrosc 27:352, 1973.
Van Dyck PM, Van Grieken RE. Anal Chem 52:1859, 1980.
Van Dyck P, Markowicz A, Van Grieken R. X-ray Spectrom 9:70, 1980.

Copyright 2002 Marcel Dekker, Inc.


Van Dyck P, Markowicz A, Van Grieken R. X-ray Spectrom 14:183, 1985.
Van Dyck PM, Torok SB, Van Grieken RE. Anal Chem 58:1761, 1986.
Van Espen P, Janssens K, Nobels J. J Chemom Intell Lab Syst 1:109, 1997.
Van Espen P, Vant dack L, Adams F, Van Grieken R. Anal Chem 51:961, 1979.
Wegrzynek D, Holynska B, Pilarski T. X-ray Spectrom 22:80, 1993.
Yap CT, Kump P, Tang SM, Wijesinghe L. Appl Spectrosc 41:80, 1987.

Copyright 2002 Marcel Dekker, Inc.