SPECTROCHIMICA

ACTA
PART B

ELSEVIER SpectrochimicaActa Part B 53 (1998) 43-48

A comparison of the performance of a fundamental parameter method

for analysis of total reflection X-ray fluorescence spectra and
determination of trace elements, versus an empirical
quantification procedure
Dariusz W~grzynek, Barbara Hotyfiska*, Beata Ostachowicz
Faculty of Physics and Nuclear Techniques, University of Mining and Metallurgy, AI. Mickiewicza 30, 30-059 Krakdw, Poland
Received 31 July 1997; revised 11 November 1997; accepted 20 November 1997

Abstract

The performance has been compared of two different quantification methods - - namely, the commonly used empirical
quantification procedure and a fundamental parameter approach - - for determination of the mass fractions of elements in
particulate-like sample residues on a quartz reflector measured in the total reflection geometry. In the empirical quantification
procedure, the spectrometer system needs to be calibrated with the use of samples containing known concentrations of the
elements. On the basis of intensities of the X-ray peaks and the known concentration or mass fraction of an internal standard
element, by using relative sensitivities of the spectrometer system the concentrations or mass fractions of the elements are
calculated. The fundamental parameter approach does not require any calibration of the spectrometer system to be carried out.
However, in order to account for an unknown mass per unit area of a sample and sample nonuniformity, an internal standard
element is added. The concentrations/mass fractions of the elements to be determined are calculated during fitting a modelled
X-ray spectrum to the measured one. The two quantification methods were applied to determine the mass fractions of elements
in the cross-sections of a peat core, biological standard reference materials and to determine the concentrations of elements in
samples prepared from an aqueous multi-element standard solution. © 1998 Elsevier Science B.V.

Keywords: Total reflection X-ray fluorescence; Trace element determination; Spectra fitting; Fundamental parameter method

I. Introduction spectrometry (FAAS), electro-thermal atomic absorp-

Nowadays, total reflection X-ray fluorescence
(TXRF) spectrometry is applied extensively for the
determination o f trace elements in various kinds o f
sample. The capabilities o f the TXRF method can
compete with other advanced instrumental analytical
techniques such as flame atomic absorption
* Corresponding author.
tion spectrometry (ET-AAS) and inductively coupled
plasma atomic emission spectrometry (ICP-AES) [1].
For most o f the elements, because o f very low mass
per unit area o f the sample, the absorption and
enhancement effects can be neglected, making the
quantification procedure fast and simple. In spite o f
these advantages, still there is room for improvements
in spectrometer design as well as in quantification
procedures. In this paper we present a fundamental

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44 D. Wqgrzyneket aL/Spectrochimica Acta Part B 53 (1998) 43-48
parameter approach applied to the determination of
trace elements by the TXRF technique. A detailed
description of this approach has been given
elsewhere [2]. In the present paper, a comparison of
the fundamental parameter (FP) method and the
empirical quantification (EQ) procedure is given.
Both methods were applied for the determination of
elements in samples prepared from peat core layers,
biological standard reference materials, and an
aqueous solution. The comparison of both quantifi-
cation methods was performed on samples selected
in such a way they contained elements giving strong
interferences in the X-ray spectra collected, namely
titanium-barium and arsenic-lead, and were also
abundant in low-Z elements such as potassium and
calcium.
2. Theoretical
2.1. Empirical quantification method
A commonly used empirical quantification proce-
dure requires the spectrometer set-up to be properly
calibrated with the use of samples prepared from
standard solutions [3]. In the process of calibration,
the ratios of elemental sensitivities to that of an
internal standard element are calculated and relative
sensitivity curves are obtained.
It should be noted that these relative sensitivity
curves have to be established from measurements
of standard samples containing two groups of ele-
ments: i.e., elements detected by their K-series and
elements detected by their L-series characteristic
radiation [3]. Both groups of elements have to be
present in calibration standards. Owing to different
values of fluorescence yields, photoelectric cross-
sections and other parameters for the K- and L-series,
the relative sensitivities of the elements determined
with the use of K-series peaks and L-series peaks
form two distinct calibration curves. For example,
the analysis of mercury, an element detected by
its L-series radiation, could not be performed if
the set of the calibration standards used to obtain
the relative elemental sensitivities contained only
elements giving K-series characteristic peaks.
Knowing the concentration or mass fraction of an
internal standard, added to the sample prior to the
measurements, the concentrations/mass fractions of
the elements in unknown samples are determined.
Before applying the procedure described above one
has to deconvolute the measured X-ray spectra of both
the investigated and standard samples in order to
obtain the net intensities of the characteristic peaks.
In this study, the Quantitative X-Ray Analysis System
(QXAS) software package [4] including the AXIL
program [5] has been used to perform all of the
calculations necessary in the empirical quantification
procedure.
2.2. Fundamental parameter method
The fundamental parameter approach used applies
a theoretical model of the acquired X-ray fluorescence
spectrum given as a function of the concentrations/
mass fractions of elements present in the analysed
sample [2]. The concentrations/mass fractions of
the elements to be determined are obtained by fitting
the model to the acquired X-ray fluorescence spec-
trum of a sample. The modelling function takes
into account measurement conditions, modification
of the excitation radiation on its way to the sample,
detector efficiency, low-energy tailing of X-ray
peaks, natural widths of the characteristic lines, the
presence of escape peaks and the presence of peaks
resulting from the most intense radiative Auger
transitions [6-10]. Since the sample analysed is
assumed to form a thin, particle-like residue on a
quartz reflector, absorption and enhancement correc-
tion factors are not included in the model. The avail-
able fundamental parameter data allow the procedure
to be used for the determination of elements with
atomic number from Z = 11 to Z = 92 [11-14]. The
concentrations or the mass fractions of the elements
are determined during a spectra-fitting procedure
taking into account all of the intensities of K-series
and/or L-series characteristic peaks of elements
present in the acquired spectrum. In this approach
an internal standard element has still to be added
to the sample before measurement, to account for
the unknown mass per unit area of the sample and
irreproducible measurement geometry. Determina-
tion of the concentrations/mass fractions of ele-
ments by the fundamental parameter method was
performed with the use of a home-made computer
program.
 D. Wggrzynek et al./Spectrochimica Acta Part B 53 (1998) 43-48 45

3. Experimental Bamsted/Thermolyne). The volumes of samples

3.1. Instrumentation and experimental arrangement
All measurements were performed with a modified
TXRF module, constructed in the Atominstitut der
Ostereichischen Universit~iten [15,16], attached to a
molybdenum-anode long fine-focus X-ray tube
(Philips PW 2275/20). A 50/zm molybdenum filter
was placed in the front of the X-ray tube window.
The tube was operated at 55 kV and 40 mA. The
X-ray fluorescence spectra were collected by an
Si(Li) detector of energy resolution equal to
170keV at 5.9keV and a Canberra SI00 multi-
channel analyser.
3.2. Preparation of samples
All of the reagents used in the process of sample
preparation were of the highest analytical grade
(Fluka, Merck). Suprapure nitric acid was addi-
tionally sub-boiled (Ktirner Analysentechnik) and
water was distilled twice and deionised (EASYpure,
pipetted onto quartz reflectors were optimised to
keep the total count rate at moderate levels and to
prevent distortion of the X-ray spectra collected.
Three groups of samples were prepared: i.e., cross-
sections taken from a peat core, biological standard
reference materials and aqueous multi-element
standard solutions.
Two peat core layers, previously freeze-dried and
powdered, were taken for analysis. The samples,
weighing 300 mg each, were digested in a Teflon
bomb with a mixture of nitric and hydrofluoric acids
with the addition of hydrogen peroxide. The digested
samples were spiked with selenium as internal
standard element. Then, three 5/~1 sub-samples were
taken from each peat solution and pippetted onto
siliconised quartz reflectors, dried in a vacuum
desiccator and measured for 2000 s.
The second group of samples to be analysed was
prepared from biological standard reference materials,
IAEA 350 Tuna Fish Flesh and a Polish standard
reference material Cabbage Leaves CL-1. A mass of
400 mg of the Tuna Fish Flesh standard was digested

Table 1
The mass fractions o f the elements in two peat core sections obtained b y T X R F using the empirical quantification method and the fundamental
parameter algorithm

Element Peat core layer sample 1 Peat core layer sample I1

Empirical quantification Fundamental parameter Empirical quantification F u n d a m e n t a l parameter

method method method method

[#g/g]

K 289 -+ 24 320 -+ 37 1754 + 165 1845 ± 174

Ca 1028 ± 34 1065 _+ 30 655 ± 30 675 ± 70
Ti 89.7 _+ 1.4 99.2 _+ 1.3 583 ± 18 644 _+ 17
V 1.8 + 0.3 3.1 ± 0.7 10.0 +_ 0.4 I 1.4 ± 0.2
Cr 3.3 _+ 0.3 4.4 _+ 0.5 9.8 ± 1.1 12.6 ± 1.8
Mn 4.8 ± 0.3 6.4 -+ 0.2 12.0 ± 0.3 13.3 ± 0.4
Fe 588 -+ 3 644 -+ 3 871 ± 33 958 ± 39
Ni 1.4 +- 0.2 1.8 -+ 0.2 6.6 ± 0.8 8.6 -+ 1.0
Cu 5.0 -+ 0.3 5.5 ± 0.4 10.2 ± 0.5 12.4 -+ 0.6
Zn 88.0 + 1.0 95.8 ± 0.9 85.6 ± 5.0 91.7 ± 5.4
As 1.7 + 0.3 1.6 ± 0.2 5.5 + 0.3 6.1 ± 0.2
Rb 1.3 ± 0.1 1.2 +_ 0.1 7.4 + 0.7 8.0 ± 0.8
Sr 7.7 + 0. I 8.5 ± 0.1 12.0 +_ 0.7 12.9 ± 0.8
Zr n.d. < LOD n.d. 24.2 + 2.0
Ba 8.3 ± 1.5 8.0 -+ 0.8 27.3 + 8 331. + 4.7
Pb 42.97 ± 1.51 38.7 ± 1.1 103 ± 9 92 + 7

n.d. - - not determined, because the relative sensitivity value for zirconium was not established
L O D - - limit o f detection.
46 D. Wegrzynek et al./Spectrochimica Acta Part B 53 (1998) 43-48
Table 2
The mass fractions of the elements in IAEA-350 Tuna Fish Flesh standard reference material obtained by TXRF using the empirical
quantification method and the fundamental parameter algorithm
Element 1AEA-350Tuna Fish Flesh
Empirical quantification method
Ca 160 _+ 10
Fe 68.3 -+ 0.4
Ni 1.4 _+ 0.5
Cu 3.4 _+ 0.6
Zn 18.1 _+ 1.2
As 4.38 + 0.01
Se 4.6 + 0.2
Rb 2.3 + 0.1
Hg 2.9 _+ 0.1
in a Teflon bomb with nitric acid. The digested sample
was spiked with yttrium as internal standard. Three
3 #1 sub-samples were pipetted onto siliconised
quartz reflectors. To prevent the losses o f mercury
which was present in the Tuna Fish standard,
2/zl volume o f an 0.1% ammonium-pyrrolidine-
dithiocarbamate (APDC) water solution was addition-
ally pipetted onto the quartz reflectors. The quartz
reflectors with samples were left to dry on a clean
bench under atmospheric pressure and then measured
for 2000 s. For analysis o f the Cabbage Leaves
standard, a 230 mg sample was taken and digested
under the same conditions as before. After digestion
the sample was spiked with selenium and volumes
o f 2/zl were pipetted on to three siliconised quartz
reflectors, dried in a vacuum desiccator and measured
for 2000 s.
The multi-element aqueous solution was prepared
from Merck single-element standard solutions o f
barium, titanium, arsenic, lead and selenium. The
1000/xg/ml standard solutions were diluted in such a
way as to obtain a solution of the following concen-
trations o f elements: Ti - - 10/~g/ml, Ba - - 2/zg/ml,
Pb - - 10/~g/ml, As - - 2/zg/ml and Se - - 2 #g/ml.
4. Results and discussion
The results of the analyses are presented in
Tables 1-4. As can be seen, the concentrations/
mass fractions determined by the empirical quantifi-
cation procedure agree well with those determined
Fundamentalparameter method Certifiedconfidence interval
[/~g/g]
140 _+ 10 (72-191)
73.2 -+ 0.3 (66.7 77.3)
1.5 _+ 0.4 (0.32 1.13)
3.7 _+ 0.6 (2.55 3.10)
18.1 _+ 1.2 (16.6 18.5)
4.69 _+ 0.02 (2.50-5.71)
4.6 _+ 0.2 (4.40 5.95)
2.3 + 0.1 (2.41 3.40)
3.5 + 0.2 (3.31 4.42)
by the fundamental parameter algorithm. Small
systematic differences can be observed in the case
o f the results shown in Table 1 and Table 3, where
most o f the mass fractions obtained by the funda-
mental parameter method are slightly higher than
those obtained by the empirical quantification proce-
dure. However, both sets of results agree well taking
into account the values o f uncertainties, except for
elements giving strongly interfering characteristic
lines such as T i - B a and A s - P b . For the other results
shown in Tables 2, and 4 the systematic differences
do not appear, except for iron for which the mass
fraction shown in Table 2 obtained by the FP algo-
rithm is higher than that obtained by EQ. The results
of the analyses o f standard reference materials
presented in Table 2 and in Table 3 indicate that
the mass fractions o f the elements obtained by the
FP algorithm match the certified confidence intervals
slightly better than the mass fractions calculated with
use o f the EQ method. From the 17 determinations
produced by the FP algorithm 11 fit the certified
confidence intervals, whereas for the results obtained
by the EQ procedure eight fall within the range o f
the certified confidence intervals. These small, not
very distinctive or decisive, systematic differences
between the results obtained by both methods may
have their source in the different algorithms used
for deconvolution of the spectra. In the case of the
EQ method applied by us, the net intensities of
K~ or L~ characteristic peaks were used to calculate
the concentrations or mass fractions o f the elements,
whereas the FP method uses an advanced home-made
 D. Wggrzynek et al./Spectrochimica Acta Part B 53 (1998) 43-48 47

Table 3
The mass fractions of the elements in CL-1 Cabbage Leaves standard reference material obtained by TXRF using the empirical quantification
method and the fundamental parameter algorithm

Element CL-1 Cabbage Leaves

Empirical quantification method Fundamental parameter method Certified confidence interval

[mg/g]
K 20.6 ÷ 0.4 21.0 _+ 0.5 (24.4-28.0)
Ca 6.0 +_ 0.1 6.0 + 0.1 (5.3 7.2)
[~g/g]
Mn 51.4 _+ 0.8 59.0 _+ 0.9 (55.5-59.7)
Ni 1.9 -+ 0.4 2.1 _+ 0.5 (2.7-3.3)
Cu 3.4 _+ 0.3 3.9 _+ 0.4 (3.1 3.6)
Zn 35.8 -+ 1.2 38.5 +- 1.3 (36.6-40.4)
Rb 37.2 -+ 0.4 40.9 -+ 0.5 (38.0-44.8)
Sr 21.8 + 0.4 24.0 +- 0.4 (14.9-26.3)

program taking into account all K-series or L-series
X-ray peaks to calculate the concentrations/mass
fractions of the elements. However, it should be
noted that in other implementations of the EQ algo-
rithm, bundled with commercial TXRF spectrometers
such as the EXTRA II (Rich. Seifert and Co.,
Ahrensburg, Germany), all the K-series or L-series
X-ray peaks are used in the course of the analytical
procedure.
As can be seen from Table 4 in the case of the
analysis of an aqueous solution containing two pairs
of elements giving strongly interfering X-ray peaks
(Ti-Ba and As-Pb), the concentrations of the ele-
ments obtained by both methods do not differ signifi-
cantly. The exception is titanium, for which the result
obtained by the EQ method is about 10% lower than
the true value and the value obtained by the FP algo-
rithm. A similar tendency can be observed for the
analysis results of real samples such as the peat core
sections shown in Table 1. These systematic differ-
ences in titanium content could originate either from
a shift between the empirical sensitivity value used
in the EQ procedure and that calculated in the FP
algorithm, or from the fact that different spectra-
fitting algorithms were used to obtain net peak areas
in both methods. As can be seen from Table 3, both
algorithms do not give good values for the mass
fraction of potassium, the lightest element analysed.
This is probably caused by absorption of the charac-
teristic radiation of potassium in the analysed sample,
which was not corrected by either of the methods
studied.
5. Conclusions
As can be seen from the results presented, both
methods of quantitative analysis give concentrations

Table 4
The concentrations of the elements in an aqueous multi-element solution containing known amounts ofTi, Ba, As, Pb and Se obtained by TXRF
using the empirical quantification method and the fundamental parameter algorithm

Element Multi-element solution

Empirical quantification method Fundamental parameter method Known concentration

[mg/1]

Ti 9.1 _+ 0.1 10.2 -+ 0.1 10.0

Ba 2.0 +_ 0.2 2.0 -+ 0.1 2.0
As 1.89 + 0.01 1.87 + 0.01 2.0
Pb 10.2 _+ 0.2 9.6 _+ 0.2 10.0
Se internal standard 2.0
48 D. Wggrzynek et al./Spectrochimica Acta Part B 53 (1998) 43-48
or mass fractions o f the elements that agree well
within the values o f uncertainties. In the case of
samples with a simple matrix the results are almost
identical (aqueous solution), whereas for samples
with complex matrix or samples containing higher
abundances o f low-Z elements the FP algorithm
seems to perform slightly better than the empirical
quantification procedure. On the other hand, the
differences in the performance o f these quantifica-
tion procedures are not significant compared with
the complexity o f the FP approach. The FP algorithm
is more complex than the empirical quantification
procedure, but when developed it can easily be
applied. The advantage o f the FP algorithm is that it
produces results o f the same accuracy and quality as
the EQ method but without the need for any calibra-
tion procedure. The FP algorithm does not even need
sensitivity values which have to be determined for EQ
methods. Also, the advantage o f the FP method is that
the FP algorithm utilises the intensities o f all K-series
or L-series characteristic peaks to calculate the con-
centrations/mass fractions of elements, whereas our
EQ method takes into account only the net intensities
of K~ or L~ peaks. This makes the FP algorithm more
suitable for the analysis of samples with a complex
matrix producing X-ray spectra with strongly interfer-
ing characteristic peaks.
Acknowledgements
This work was partially supported by the State
Committee for Research, grant no. 11.220.01.
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