Nuclear Instruments and Methods in Physics Research B 364 (2015) 85–92

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Nuclear Instruments and Methods in Physics Research B

journal homepage: www.elsevier.com/locate/nimb

X-ray spectrometry and X-ray microtomography techniques for soil

and geological samples analysis
A. Kubala-Kukuś a,b,⇑, D. Banaś a,b, J. Braziewicz a,b, M. Dziadowicz a, E. Kopeć a, U. Majewska a,b,
M. Mazurek a, M. Pajek a, M. Sobisz a, I. Stabrawa a, J. Wudarczyk-Moćko b, S. Góźdź b,c
a
Institute of Physics, Jan Kochanowski University, ul. Śwießtokrzyska 15, 25-406 Kielce, Poland
b
Holycross Cancer Center, ul. Artwińskiego 3, 25-734 Kielce, Poland
c
Institute of Public Health, Jan Kochanowski University, IX Wieków Kielc 19, 25-317 Kielce, Poland

a r t i c l e i n f o a b s t r a c t

Article history: A particular subject of X-ray fluorescence analysis is its application in studies of the multielemental sam-
Received 20 September 2014 ple of composition in a wide range of concentrations, samples with different matrices, also inhomoge-
Received in revised form 19 June 2015 neous ones and those characterized with different grain size. Typical examples of these kinds of
Accepted 2 July 2015
samples are soil or geological samples for which XRF elemental analysis may be difficult due to XRF dis-
Available online 13 August 2015
turbing effects. In this paper the WDXRF technique was applied in elemental analysis concerning differ-
ent soil and geological samples (therapeutic mud, floral soil, brown soil, sandy soil, calcium aluminum
Keywords:
cement). The sample morphology was analyzed using X-ray microtomography technique. The paper dis-
Soil and geological samples
Wavelength dispersive X-ray fluorescence
cusses the differences between the composition of samples, the influence of procedures with respect to
analysis the preparation of samples as regards their morphology and, finally, a quantitative analysis. The results of
Matrix effects the studies were statistically tested (one-way ANOVA and correlation coefficients). For lead concentration
X-ray microtomography determination in samples of sandy soil and cement-like matrix, the WDXRF spectrometer calibration was
X-ray powder diffraction performed. The elemental analysis of the samples was complemented with knowledge of chemical com-
position obtained by X-ray powder diffraction.
Ó 2015 Elsevier B.V. All rights reserved.

1. Introduction determining geochemical till properties. Thus it is also possible

The well-known X-ray spectrometry (XRF) technique [1–5]
allows fast and accurate simultaneous analysis of many elements.
It is routinely used in different applications to study the elemental
composition of the samples [6–9]. A particularly, often this tech-
nique is used in studies of the multielemental sample of the com-
position in a wide range of concentrations, samples with different
matrices, also inhomogeneous ones and those characterized with
different grain size. Typical examples of these kinds of samples
are soil or geological matrix samples (soil, till, sand, sediment
and mineral). The elemental and chemical analysis of soil and geo-
logical samples is applicable in many fields of science, e.g. in agri-
culture, biology or geography [6,7,9–11]. One of the main and often
concidered topic of these analyses is an influence of environmental
pollution on soil heavy metals concentration. The knowledge of the
elemental composition of soil samples is also important in under-
standing of the processes of soil formation, soil erosion and in
⇑ Corresponding author at: Institute of Physics, Jan Kochanowski University, ul.
ß tokrzyska 15, 25-406 Kielce, Poland.
Świe
to compare the composition and morphology of different samples
in the study of their origin and the reconstruction of their geohis-
tory. In the quantitative description of the phenomena the chemi-
cal composition of the sample is also important.
Despite the many advantages, however, XRF technique has
shortcomings, e.g. so-called matrix effects and particle-size effects
to name a few [3,4]. These interfering effects, which can seriously
constrain the accuracy of the qualitative and quantitative XRF anal-
ysis, are caused by variations in the fluorescence intensities of the
excited elements due to the chemical composition and granulation
of the sample. In general, disturbing effects can be classified as:
interelement radiation, the matrix effects, particle-size effects
(grain-size effects, granulation effects) and mineralogical effects
[3,4]. These effects influence both the intensity of characteristic
X-ray and X-ray scattering radiation which mainly determine the
continuous background observed in the measured X-ray spectrum.
The scattered radiation may disturb the analysis, especially when a
low concentration is determined. Weak signals of the characteris-
tics radiation can be obscured by a strong background due to scat-
tered radiation. Selecting optimum measurement conditions for X-

http://dx.doi.org/10.1016/j.nimb.2015.07.136
0168-583X/Ó 2015 Elsevier B.V. All rights reserved.
86 A. Kubala-Kukuś et al. / Nuclear Instruments and Methods in Physics Research B 364 (2015) 85–92
ray fluorescence determination of a particular element in a given
material requires information concerning the chemical composi-
tion and the expected concentration ranges of all sample con-
stituents in all analyzed samples.
In a typical XRF sample preparation procedure, the analyzed
material is crushed, ground (with different milling time) and
formed as pellet (using different pressure). Sometimes different
wax binders are used in the pellet formation process. The appropri-
ate sample preparation procedure can reduce the disturbing
effects.
The aim of the presented study was the analysis of the soil and
geological samples with different matrices using the wavelength
dispersive X-ray fluorescence technique (WDXRF) [3]. The samples
had different elemental composition, grain sizes and different
material packing. The main motivation of the undertaken research
topic was the improvement of the qualitative and quantitative
analysis of the materials with a particular kind of matter, namely,
the soil and geological materials, and study of the influence of the
preparation procedure on sample morphology and next on the
reduction of XRF disturbing effects. The WDXRF elemental analysis
was complemented with chemical composition analysis using the
XRPD technique [12]. The morphology of each sample, especially
sample grain size, was characterized in the micrometers scale
using X-ray microtomography technique [13]. The obtained results
of the analysis of the soil and geological samples were interpreted
in the context of influence of the sample matrix on the elemental
quantitative analysis. Additionally, some practical aspects of this
analysis were discussed. The measurements were done with the
WDXRF spectrometer – AXIOS (Panalytical) [14], X-ray diffrac-
tometer X’Pert (Panalytical) [15] and X-ray microtomograph
SkyScan 1172 [16]. The first part of the paper describes the sam-
ples and the preparation procedure. Next, the experimental devices
and measurement conditions are discussed. A further part of the
work concentrates on the obtained results and discussion. The sec-
tion conclusion summarizes WDXRF, XRPD and X-ray microtomog-
raphy studies of soil and geological samples. The results obtained
can be used to improve the accuracy and reliability of the XRF
measurements.
2. Sample description and preparation procedure
2.1. Sample description
Soil and geological samples which were analyzed in presented
studies have been chosen taking into account their different matri-
ces, it was namely: peloid (therapeutic mud), floral soil, brown soil,
sandy soil and calcium aluminium cement samples.
Peloid in form of mud or clay is used in balneotherapy and ther-
apeutic bathing. Is used in the treatment of rheumatic diseases,
gynecological diseases and certain diseases of the internal organs.
Laboratory processed mud is a raw material for the production of
various kinds of medicines and cosmetics. The samples of peloid
analyzed under the presented studies came from a Polish health
resort Solec Zdrój located in the south-central part of Poland.
Floral soil samples were commercially available different soil
samples standard used in the cultivation of potted plants, while
samples of brown soil (main type of soil in Poland) came from a
leafy forest from southern Poland.
Sandy soil was a test sample of Worldwide Open Proficiency
Test for X-ray Fluorescence Laboratories PTXRFIAEA10 [17] orga-
nized by the IAEA Nuclear Science and Instrumentation
Laboratory in Seibersdorf, Austria. Sandy soil material, prepared
and tested by an external independent laboratory, was as a pow-
dered, homogenized, and dried material distributed to laboratories
in order to determine the mass fractions of chemical elements
making up the sample according to their routine analytical
procedures.
The last sample was calcium aluminium cement which is a
hydraulic binder used for the concretes and prefabricated ele-
ments, in heating devices operating up to a temperature of
1600 °C, in a special industrial building, in building chemistry as
a component of mortars, in mining and in individual reparation
and installation works (stacks, ventilation, fireplaces). Such exten-
sive use of calcium aluminium cement is possible due to its special
properties, such as: a short bonding time, rapid increase in
mechanical strength and resistance to aggressive sulfate, sea
water, carbon oxide, methane, the ability to use under subzero
temperatures ( 10 °C). Typical chemical composition of this mate-
rial is as follows: Al2O3 (minimum 40%), CaO (minimum 36%), SiO2
(3–6%), Fe2O3 (8–12%) and mineralogical basic phase is calcium
monoaluminate. Sandy soil and calcium aluminum cement sam-
ples, for which elemental composition was known, can be used
in presented studies as a reference materials.
2.2. Sample preparation procedure
For the wavelength dispersive X-ray fluorescence analysis
(WDXRF) the samples had to be prepared as a pellet. Prior to pellet
formation, the samples analyzed in the presented studies (thera-
peutic mud, floral soil and brown soil samples) were dried and
ground with the compact ball mill (MiniMill2) at the rotation
speed 300 rpm and different grinding time t = 1, 2, 3 and 6 min.
The sandy soil and calcium aluminium cement samples did not
require grinding. Next, the ground samples of 5–10 g were formed
to the pellet. Usually in pellet formation the pelletizing pressure
was 100 kN but for brown soil sample milled for 6 min additional
pressure of 150 kN and 200 kN was applied. In general, it was
expected that proposed sample preparation will result with the
reduction of grain-size effect appearing for soil and geological sam-
ples. Calcium aluminium cement samples were also prepared by
adding to the sample a wax binder (C18H36O2N2) whose mass
was from 1% to 7% of the sample mass. The aim of the above test
was to check influence of the amount od added binder on the on
the quantitative analysis of the studied geological samples. Next,
the elemental composition of prepared pellets was analyzed using
the WDXRF method.
2.3. Experiment
The WDXRF analysis was performed using the AXIOS spectrom-
eter (Panalytical) equipped with an Rh-anode X-ray tube with
maximum power of 2.4 kW. The wavelength dispersive system of
the spectrometer used five crystals (LiF (2 0 0), Ge (1 1 1), PE
(0 0 2), PX1 and LiF (2 2 0)), which were automatically selected dur-
ing the measurements. The characteristic X-rays induced in the
sample were diffracted on one of the crystals and measured by
flow proportional counter for optimal detection of elements up
to Fe or a scintillation detector for heavier elements. In order to
cover the X-ray energy (wavelength) range of the interest it was
necessary to perform 12 scans with different diffraction crystal-
detector configurations. Energy resolution of the setup (10–
50 eV) allows for unambiguous identification of element intensity
even for very rich in elemental composition samples. The measure-
ments were performed in vacuum. The quantitative analysis of the
spectra was performed with the PANalytical analytical program
Omnian [14]. The Omnian package is available for the standardless
analysis of all types of samples. Omnian includes advanced algo-
rithms designed to profile known limitations inherent to XRF and
includes spectral interference. The darkmatrix correction provides
better accuracy in cases where light elements such as C, H and O
contribute to significant absorbance. In generally, corrections
 A. Kubala-Kukuś et al. / Nuclear Instruments and Methods in Physics Research B 364 (2015) 85–92 87

which were involved in Omnian quantitative analysis of studied

sample were as follows: (a) finite thickness (correction where the
sample was not infinite thick for all measured energies), (b)
Compton validation factor (the analysis of unmeasured matrix
compounds by using the peak of Compton-scattered primary X-
ray beam, (c) compound list (enables to select a compound list
when compounds such as oxides, sulphide, etc. instead of elements
are analyzed), (d) sample preparation (enables to define sample
preparation parameters such as binders, fluxes and sample
weights). The morphology of the analyzed samples was character-
ized in micrometers scale, especially in the context of the informa-
tion about grains size, using X-ray microtomography technique
(tomograph SkyScan 1172). The maximum size of the scanned
object can be 70 mm (in height) and 35 mm (in diameter) in stan-
dard measurement. Source of the radiation is W anode X-ray tube
air cooled, with Umax = 80 kV and Imax = 100 lA. Multiple 2D X-ray
images are stored by a digital CCD camera coupled to the scintilla-
tion screen (11 Mpix) while the sample is rotated. Spatial resolu-
tion of SkyScan 1172 is about 5 lm. Applied reconstruction
algorithm: reconstruction of cone-shaped beam using Feldkamp
method.
The X-ray powder diffraction measurements were performed in
Bragg–Brentano geometry using X’Pert Pro MPD diffractometer
Fig. 1. An example of the WDXRF spectrum of therapeutic mud sample excited
(PANalytical). This diffractometer is equipped with a Cu anode
with the primary X-rays generated in a Rh-anode X-ray tube operated with voltage
1.8 kW X-ray tube with a linear exit window and PW3050/60 U = 24 kV and current I = 100 mA. The presented spectrum (scan) was measured in
goniometer with an angular resolution of 0.001°. For X-rays, dif- an energy range from 2.2 keV to 2.6 keV using Ge (1 1 1) crystal (2d = 0.6532 nm).
fracted on an analyzed sample, position sensitive silicon strip Characteristic X-rays were detected by a flow counter. The conditions concerning
detector (X’Celerator) with dimensions 15  9 mm and 128 strips the sample preparation procedure are also given inside the figure.

was used. The detector speeds up the data collection by measuring

simultaneously about 2° of 2h. The measurements were performed
in the 2h angular range from 5° to 70°. Typical measurement time
of one full angular scan was about 30 min. The obtained diffrac-
tograms were analyzed qualitatively with the Highscore 3.0e pro-
gram using the PDF-2 Release 2009 database of the International
Centre for Diffraction Data.

3. Results and discussion

The application of the WDXRF allowed for elemental analysis

from oxygen (O) to lead (Pb) in a wide range of concentrations,
with detection limit on the level of about 10 lg/g. The example
of WDXRF spectrum is presented in Figs. 1 and 2, registered for
therapeutic mud and sandy soil samples, respectively. Inside the
figure the sample preparation procedure conditions were given.
The presented figures are one of the twelve spectra measured for
each sample and cover only part of energy of characteristic X-ray
emitted from the sample. As can be easily seen the element fluo-
rescence lines are very well separated. In the case of the therapeu-
tic mud the spectrum presents the Ka and Kb lines of sulfur. Rh
lines come from primary X-ray beam. In the sandy soil spectrum
the following lines are identified: K–Kb, Ca–Ka, Ca–Kb, Ba–La and
Ti–Ka. In the Fig. 2, for comparison, also spectrum of this sandy soil Fig. 2. An example of the WDXRF spectrum of sandy soil sample excited with the
sample measured by TXRF technique (energy dispersive analysis) primary X-rays generated in a Rh-anode X-ray tube operated with voltage U = 24 kV
is presented. The main property of the spectrum is low energy res- and current I = 100 mA. The presented spectrum (scan) was measured in an energy
olution resulting in interferences of characteristic X-ray lines, like range from 3.5 keV to 4.7 keV using LiF (2 0 0) crystal (2d = 0.4028 nm). The
for example for Ba–La and Ti–Ka lines, or for K–Kb and Ca–Ka lines. characteristic X-rays were detected by flow counter. For comparison also EDXRF
spectrum of this sample measured by TXRF technique is presented in Figure.
The elemental analysis gave information of many elements (Al,
As, Ba, Ca, Ce, Cl, Cr, Cu, Fe, Ga, K, Mg, Mn, Na, Nb, Ni, O, P, Pb, Rb, S,
Si, Sr, Ti, V, Y, Zn and Zr) in a wide range of concentration values elements are included. The total uncertainty of the WDXRF analy-
(from about 10 lg/g to about 30%). The results of the quantitative sis is equal to the sum of the variances of all the individual sources
analysis for main elements Na, Mg, Al, Si, P, S, K, Ca and Fe are pre- of uncertainty, random (mainly counting statistics), systematic
sented in Table 1. Samples, for which element concentrations are (sample preparation, absorption, secondary X-ray enhancement,
shown in this Table, were ground for 3 min (mud, floral soil, brown particle effects and calculation of the results) [3]. In WDXRF mea-
soil) and formed under the pressure of 100 kN. In the Table also surements the uncertainty of sample weight measurement was
experimental uncertainties and sum of concentration of presented negligible. Finally, the experimental uncertainty was determined
88 A. Kubala-Kukuś et al. / Nuclear Instruments and Methods in Physics Research B 364 (2015) 85–92

Table 1
Concentration (%) of Na, Mg, Al, Si, P, S, K, Ca and Fe elements in soil and geological samples. Mud, floral soil and brown soil samples were grinding 3 min before pellets formation
in which 100 kN pressure was applied. In the table also experimental uncertainties and sum of the elements concentration are given.

Sample – concentration (%)

Element Mud Floral soil Brown soil Sandy soil Cement
Na 0.015 ± 0.004 0.015 ± 0.001 0.085 ± 0.008 0.516 ± 0.046 0.032 ± 0.006
Mg 0.032 ± 0.005 0.039 ± 0.006 1.80 ± 0.040 0.086 ± 0.0118 0.155 ± 0.012
Al 0.127 ± 0.011 0.136 ± 0.011 10.2 ± 0.098 2.05 ± 0.100 22.9 ± 0.151
Si 0.231 ± 0.014 0.785 ± 0.002 27.8 ± 0.174 39.8 ± 0.640 1.23 ± 0.037
P 0.022 ± 0.004 0.051 ± 0.013 0.025 ± 0.006 0.146 ± 0.009 0.020 ± 0.005
S 0.200 ± 0.013 0.189 ± 0.027 0.010 ± 0.004 0.040 ± 0.007 0.087 ± 0.010
K 0.017 ± 0.004 0.146 ± 0.011 2.10 ± 0.054 0.943 ± 0.052 0.038 ± 0.007
Ca 0.849 ± 0.028 2.72 ± 0.049 2.54 ± 0.060 0.335 ± 0.028 24.9 ± 0.174
Fe 0.145 ± 0.011 0.109 ± 0.010 4.63 ± 0.086 0.610 ± 0.033 9.17 ± 0.113
Sum 1.64 4.19 49.2 44.5 58.5

mainly by counting statistics, and for major elements (>1% of con-
centration) is 2–5% and for minor elements (about 0.1% of concen-
tration) it is 10–15%. For elements with concentration at about
0.01% the uncertainty is 10–20%, while for the lowest measured
concentrations (about 0.001%) it is about 50%. Taking the latest
observation into account, element concentration equal to 0.001%
(10 lg/g) is a detection limit of the applied WDXRF technique.
On the other hand for the concentration on the level of tens of per-
cent the experimental uncertainty is below 1%.
As it can be interpreted from the table therapeutic mud and flo-
ral soil are materials with low Z (atomic number) matrix. The total
concentrations of the determined elements are relatively low, i.e.
only 1.64% and 4.19%, respectively. The matrix of these samples
are build mainly from light organic elements (H, C, N and O) most
of which are not detected in spectrometer. It is worth noting that
relatively high concentration of sulfur in these samples is observed
comparing with the rest of samples, namely brown soil, sandy soil
and cement. The matrices of the latter materials are systematic
‘‘heavier”, for brown soil specified by high concentration of Si, Al,
Fe, Ca and K, for sandy soil by Si and Al, and for cement by Ca,
Al, Fe and Si. Also higher (from 44.5% to 58.5%), comparing to pre-
vious two materials, total sum of the discussed elements is
observed.
Differences in sample matrix can be observed in the spectra of
the primary X-ray beam scattered in the sample. The results of
such measurements are presented in the Fig. 3. The spectra were
not presented for all samples but for floral soil (three kinds), brown
soil (two kinds) and calcium aluminate cement (two samples). In
the figure Rh–Ka and Rh–Kb lines are marked together with the
corresponding Compton scattering peaks. Having considered each
spectrum ratio of the fluorescence line to its Compton scattering
peak it can be observed that spectra are of three types (correspond-
ing with three groups of samples): (1) the high intensity of the
Compton scattering peak (floral soils) – demonstrating strong scat-
tering of Rh K-lines in a light matrix, (2) the low intensity of the
Compton scattering peak (cement material) – demonstrating weak
Compton scattering and strong attenuation of Rh K-lines in a heavy
matrix, (3) an intermediate type (brown soils). In the quantitative
analysis performed with Omnian standardless calibration the peak
intensity of Compton scattering of primary X-ray can be taken into
account in the analysis of unmeasured matrix compounds. For this
purpose so-called Compton validation factor (CVF) was determined
by comparing the measured Compton scattering peak with this one
calculated on the basis of the obtained concentration. The value of
the CVF being about one, which was the case for the of analyzed
soil and geological samples, is an indication that, in quantitative
analysis, the matrix of the analyzed sample was reconstructed
properly. We have observed that for some special kind of samples,
however, this standardless Omnian calibration introduce system-
atic error that can be concluded on the basis of CVF significantly
different from one. This issues is addressed and discussed later in
presented paper.
Assuming that the percentage elemental composition is equiv-
alent to percentage concentration of the oxides typical for soil
and geological samples, namely: Na2O, MgO, Al2O3, SiO2, P2O5,
SO3, K2O, CaO and Fe2O3, the oxides concentration were calculated.
Table 2 presents concentration values of these oxides in brown soil
ground 1, 2, 3 or 6 min under 100 kN of the pelletizing pressure.
Possible dependence of the oxide concentration on the time of
grinding was checked statistically. One-way ANOVA analysis [20]

Table 2
Concentration (%) of Na2O, MgO, Al2O3, SiO2, P2O5, SO3, K2O, CaO and Fe2O3 oxides in
brown soil ground 1, 2, 3 or 6 min (100 kN pelletizing pressure). In the table also
experimental uncertainties are given.

Brown soil Concentration (%) grinding time

Oxide 1 min 2 min 3 min 6 min
Na2O 0.149 ± 0.012 0.114 ± 0.010 0.114 ± 0.010 0.106 ± 0.010
MgO 2.94 ± 0.007 2.99 ± 0.052 2.98 ± 0.052 2.94 ± 0.051
Al2O3 19.1 ± 0.131 19.2 ± 0.131 19.3 ± 0.132 19.0 ± 0.131
SiO2 60.4 ± 0.233 59.7 ± 0.232 59.5 ± 0.231 58.8 ± 0.230
P2O5 0.076 ± 0.008 0.065 ± 0.008 0.057 ± 0.007 0.064 ± 0.008
SO3 0.035 ± 0.006 0.036 ± 0.006 0.025 ± 0.005 0.031 ± 0.005
Fig. 3. Spectra of primary X-ray beam (form Rh-anode X-ray tube) interacting with
K2O 2.66 ± 0.049 2.60 ± 0.048 2.53 ± 0.048 2.59 ± 0.048
soil and geological samples with different matrix (three kinds of floral soil, two
CaO 3.18 ± 0.053 3.12 ± 0.053 3.56 ± 0.057 3.29 ± 0.054
kinds of brown soil and two kinds of calcium aluminium cement). In the figure Rh-
Fe2O3 6.59 ± 0.077 6.70 ± 0.078 6.62 ± 0.077 6.62 ± 0.077
Ka and Rh-Kb lines are marked together with the corresponding Compton
Sum 95.1 94.5 94.7 93.4
scattering peaks.
 A. Kubala-Kukuś et al. / Nuclear Instruments and Methods in Physics Research B 364 (2015) 85–92 89

was applied to study the change of oxides total concentration as a

function of grinding time values. At the significant level 0.05 the
total concentration of oxides are not statistically significant differ-
ent. The correlation between concentration and grinding time was
checked for each oxides. Fig. 4 presents dependence of SiO2 con-
centration on the grinding time. The experimental uncertainties
are on the level about 0.4% while the change of SiO2 concentration
is about 2% and only for this oxide the correlation was statistically (a) (b) (c) (d)
confirmed, with negative value of the correlation coefficient
(R = 0.962). In our opinion the correlation which we are looking
for are on low level, and only such high value of concentration,
with relatively small experimental uncertainties, as for the SiO2
let them to be observed. On the other side, because of the relatively
higher experimental uncertainties, for some oxides (for example
Na2O) obtained dependence was not confirmed. Explanation of
observed correlation for SiO2 oxide is difficult because of the com-
plexity of the phenomena occurring during X-ray interaction with
matter. One of the reasons could be the oxide phase change. As the
(e) (f) (g)
XRF studies show the intensity of the emitted from the sample
Fig. 5. X-ray microtomography images of soil pellets prepared after different times
characteristic Si X-ray depends on the SiO2 phase (assuming the of grinding: brown soil ((a) 1 min, (b) 2 min, (c) 3 min, (d) 6 min) and floral soil ((e)
same concentration of this oxide in the sample) [18]. Proposed 1 min, (f) 2 min, (g) 3 min). The pressure at the pelletizing was 100 kN.
hypothesis could be verified in dedicated X-ray diffraction analysis.
The second reason could be the impact of the presence of other ele-
ments on the intensity of Si characteristic X-ray, as for example asymptotic grain size which can be achieved in our sample prepa-
stronger excitation of Al, which concentration is relatively high ration procedure (and estimation the needed time). Additional
(about 10%) in sample of brown soil [19]. question was if and how the grain size depends on the kind of soil
The evidence of dependence of the sample morphology on the sample. On the basis of the X-ray microtomography images, the
grinding time was confirmed in X-ray microtomography measure- mean value of grains size was estimated (which was graphically
ments. Fig. 5 shows images of brown soil and floral soil pellets pre- presented in the Fig. 6). As can be observed the grain size
pared after different time of grinding (t = 1, 2, 3 and 6 min). The decreased with an increase in the milling time both for brown soil
pressure at the pelletizing was 100 kN. First observation from and floral soil. Determined grain size was from about 0.8 to
tomographic images is that floral soil is a lighter matrix sample 0.07 mm, and from 0.4 to 0.07 mm, respectively for brown and flo-
comparing to a brown soil sample, as it was also suggested based ral soil. The asymptotic value 0.07 mm was achieved after time
on the results of Table 1. Next, the homogeneity of the sample 3 min for floral soil, while for brown soil it was 6 min.
increases with increasing the milling time. The main benefits of Application of shorter grinding time reduces effect of a sample con-
tomographic measurement is, however, possibility of estimation tamination by Zr which is main component of material from which
of the grain size distribution (mean value and standard deviation mill is made. In the Fig. 6 also standard deviations of grain size are
as an information of homogeneity) and determination of the presented. It can be concluded that standard deviation is higher for

Fig. 4. Dependence of the SiO2 oxide concentration (%) on the time of material
grinding for brown soil sample. In the figure, the fitted line equation and correlation Fig. 6. The mean value of grain size estimated from X-ray microtomography images
factor R are presented. The confirmation of statistically significant correlation is for brown and floral soil samples versus grinding time. Marked uncertainties are
given by p value. standard deviations.
90 A. Kubala-Kukuś et al. / Nuclear Instruments and Methods in Physics Research B 364 (2015) 85–92

brown soil. Additionally, decreasing, as a function of grinding time, soil or calcium aluminum cement. Lead determination is one of
value of relative standard deviation results from better homogene- the main topics in elemental analysis of the soil, geological, or
ity of the sample. more general, environmental samples but applied procedure can
Possible dependence of oxides concentration in brown soil sam- be adopted to any element. Calibration samples were prepared
ples (see Table 2) on the pressure used in pellets formation by the addition to sandy soil and to cement material determined
(100 kN, 150 kN and 200 kN, t = 6 min) was checked statistically amount of the lead dioxide (PbO2) in order to get a few samples
for each oxides. In general, pressure used in pellets formation influ- with a different Pb concentration. For sandy soil material it was
ences on the characteristic X-ray intensity emitted from the sam- 5 samples with lead concentration of 0.5, 1, 3, 5 and 10 (%) and
ple, wherein the magnitude of this correlation depends of the for cement it was 0.06, 0.1, 0.2, 0.4 and 0.9 (%). The pellets were
grain size. In case of presented studies, however, only for K2O oxide formed under 100 kN pressure. In preparation of calibration sam-
concentration the correlation was statistically confirmed, with ples, the natural amount of lead in the samples was taken into
negative value of the correlation coefficient (R = 0.998). In our account (Pb = 26.3 lg/g in sandy soil, Pb = 77.8 lg/g in calcium alu-
opinion it is due to relatively small number of experimental points minium cement).
(only three values of pressure: 100 kN, 150 kN, 200 kN). For this Fig. 7 presents WDXRF spectra of sandy soil samples mixed with
reason also that topic is not discussed in detail in this paper. lead dioxide (PbO2) which amount was from 0 to 10% of sample
The results of the elemental analysis of calcium aluminium mass. The presented spectra (scans) were measured in an energy
cement samples prepared by mixing with a wax binder range from about 12.2 to 15.5 keV covering the energy of Pb–Lb,
(C18H36O2N2) whose mass was up to 7% of the sample mass are Pb–Lc, Rb–Ka and Sr–Ka fluorescence lines. Lead fluorescence lines
included in the Table 3. In quantitative analysis, performed using are very well separated up to natural lead level in the soil sandy
Omnian calibration, the concentration results were corrected for material which is closed to the detection level of the WDXRF tech-
the amount of binder. In the Table also the experimental uncertain- nique. It is also worth noting how increasing lead concentration in
ties are presented. As can be noticed, the sum of oxides concentra-
tion slowly becomes lower with an increase in the mass of the
binder. It is a result of decreasing the concentration of most of
the oxides (Na2O, MgO, Al2O3, SiO2, P2O5, SO3, CaO). Possible
dependence of the oxide concentration on the binder mass was
checked statistically. The correlation coefficients were calculated
for each oxide and negative correlation was statistically confirmed
for Al2O3 (R = 0.879), P2O5 (R = 0.886) and CaO (R = 0.981).
Main reason of the observed correlation is enhancement of scatter-
ing both of primary and secondary radiation because of binder
light element composition. Dilution of sample results in increased
levels of background and difficulty in detection of trace elements.
One-way ANOVA analysis [20] was applied to study the change
of total concentration of oxides under different binder mass. At
the significant level 0.05 total concentration of oxides is not statis-
tically different. Generally, although there are changes in the con-
centration, it can be concluded that the addition of wax binder did
not affect the quantitative analysis of the main components up to
7% of binder mass, the Omnian calibration can be applied without
necessity of preparation special quantitative calibration.
In quantitative analysis of soil and geological samples it was
observed that for matrix which component is element much heav-
ier than the other the standardless calibration introduces system-
atic error that can be concluded from observed values of
Compton validation factor being significantly different from one.
In these cases better is to performed classical calibration of spec- Fig. 7. WDXRF spectra of sandy soil samples mixed with a different amount of lead
oxide (PbO2) (from 0% to 10% of sample mass). The spectra were excited by the
trometer. In presented studies the classical calibrations for
primary X-rays generated in an Rh-anode X-ray tube operated with voltage
WDXRF spectrometer were performed for measurements of the U = 60 kV and current I = 40 mA. The presented spectra (scans) were measured in an
Pb concentration in samples whose matrices are of type of sandy energy range from about 12.2–15.5 keV and using LiF (2 2 0) crystal
(2d = 0.2848 nm).

Table 3
Concentration (%) of Na2O, MgO, Al2O3, SiO2, P2O5, SO3, K2O, CaO and Fe2O3 oxides in calcium aluminum cement samples mixed before the pellets formation with a different
amount of the binder. In Table also experimental uncertainties are included.

Calcium aluminum cement Measured compound concentration (%) for different amount of binder (%)
Oxide 3% 4% 5% 6% 7%
Na2O 0.048 ± 0.007 0.038 ± 0.006 0.035 ± 0.006 0.044 ± 0.006 0.036 ± 0.006
MgO 0.201 ± 0.013 0.200 ± 0.013 0.200 ± 0.013 0.147 ± 0.012 0.169 ± 0.012
Al2O3 42.6 ± 0.196 41.4 ± 0.193 41.9 ± 0.194 41.3 ± 0.193 40.6 ± 0.191
SiO2 2.60 ± 0.048 2.41 ± 0.047 2.47 ± 0.047 2.43 ± 0.047 2.35 ± 0.046
P2O5 0.049 ± 0.007 0.040 ± 0.006 0.039 ± 0.006 0.039 ± 0.006 0.035 ± 0.006
SO3 0.214 ± 0.014 0.189 ± 0.013 0.185 ± 0.013 0.177 ± 0.013 0.179 ± 0.013
K2O 0.044 ± 0.006 0.043 ± 0.006 0.043 ± 0.006 0.044 ± 0.006 0.044 ± 0.006
CaO 34.8 ± 0.177 34.3 ± 0.176 34.1 ± 0.175 33.9 ± 0.175 33.5 ± 0.174
Fe2O3 13.2 ± 0.109 13.0 ± 0.108 13.1 ± 0.109 13.0 ± 0.108 12.8 ± 0.108
Sum 93.8 91.6 92.1 91.1 89.7
 A. Kubala-Kukuś et al. / Nuclear Instruments and Methods in Physics Research B 364 (2015) 85–92 91

the calibration sample affects the intensity of Sr–Ka line. Based on

measured spectra the calibration curve was obtained. As an exam-
ple, in the Fig. 8 the calibration for Pb determination in sample of
calcium aluminum cement (40% of Al2O3, 36% of CaO) using the
WDXRF method is presented. Measurement conditions, the equa-
tion of linear dependence and value of correlation factor are given
in the figure. As was mentioned above sandy soil and cement sam-
ples (with mixed lead oxide) were samples of specific matrix type,
namely matrix of relative light elements with one much heavier
element (Pb). In quantitative analysis of these samples, using the
Omnian standardless calibration, the CVF was up to 1.27 for
cement and 0.75 for sandy soil samples, reflecting the complexity
of the studied samples.
In XRF technique another effects disturbing quantitative analy-
sis of elements are mineralogical effects interpreted as influence of
the type of mineral in which the analysed element occurs on the
intensity of characteristic X-ray of this element. The main reason
for mineralogical effects is simply the different absorption of the
fluorescent radiation in the particles of minerals of different chem-
ical composition. There are observed local matrix effects, taking
place within individual particles when the particle sizes are larger
than the penetrating range of photons. In studies of mineralogical
effects the X-ray powder diffraction (XRPD) technique can be suc- Fig. 9. The diffractogram of the cement sample mixed with 1% of PbO2 obtained
cessfully used. As an example we present result of the XRPD anal- with the XRPD method. Primary X-rays diffracted on the samples were generated in
ysis of cement sample used for spectrometer calibration. In Fig. 9 a Cu-anode X-ray tube operated with voltage U = 45 kV and current I = 40 mA. The
the diffractogram of the cement sample mixed with 1% of PbO2 is compound obtained in the following diffractogram: 91% of calcium aluminum oxide
(A), 8% of iron aluminum calcium oxide (B) and 1% of lead dioxide (C).
shown. The primary X-rays diffracted on the samples were gener-
ated in a Cu-anode X-ray tube operated with voltage U = 45 kV and
current I = 40 mA. In the spectrum the signals from the following
4. Conclusions
compounds were identified: about 91% of calcium aluminum
oxide, 8% of iron aluminum calcium oxide and 1% of lead oxide.
The paper discussed the application of wavelength dispersive X-
Calcium aluminum oxide is known to be the main compound of
ray spectrometry in elemental analysis of soil and geological sam-
this cement. Concluding, the XRPD is useful technique for study
ples. Taking the disturbing effects occurring in the XRF analysis
the type of phase in which the analysed element occurs. Main lim-
into account, the main motivation of the undertaken research topic
itation of this technique is, however, the detection limit of XRPD
was to improve the qualitative and quantitative analysis of the
method being on the level 1%.
materials with a particular type of matter, namely, the soil and
geological matrix materials.
In the studies, a different type of samples were investigated,
namely: therapeutic mud, floral soil, brown soil, sandy soil and cal-
cium aluminum cement. A typical WDXRF sample preparation pro-
cedure (pellet formation) was studied in details by the use of
various: times for material grinding, pelletizing pressures, and
the wax binder masses. The WDXRF spectra were discussed in
the context of element intensity fluorescence line, the ratio of
the measured primary beam Compton scattering in the analyzed
samples. Finally quantitative analysis was performed. The elemen-
tal composition of samples (with a different matrix) was com-
pared. The dependence of the results of the sample quantitative
analysis on sample preparation conditions (the grinding time, pres-
sure and binder mass) was statistically tested using the one-way
ANOVA technique and correlation coefficients. The evidence of
the dependence of the sample morphology on the grinding time
was confirmed in X-ray microtomography measurements from
which grain sizes were estimated being on the level from 0.4 to
0.07 mm. In the presented studies the calibration of the WDXRF
spectrometer for measure the concentration of Pb in samples
(whose matrices are of sandy soil or calcium aluminium cement
type) was also performed. It was demonstrated that sandy soil
and cement calibration samples with mixed lead oxide are the
samples of a specific matrix type, which analysis can be easier
applying the X-ray powder diffraction technique (sample chemical
Fig. 8. Calibration for determination of Pb concentration in samples of matrix as for
calcium aluminum cement using the WDXRF method (AXIOS spectrometer). composition). The results are of practical importance for applica-
Measurement conditions, the equation of linear dependence and the value of the tion of X-ray spectrometry in elemental analysis of soil and geolog-
correlation factor are given in the figure. ical samples.
92 A. Kubala-Kukuś et al. / Nuclear Instruments and Methods in Physics Research B 364 (2015) 85–92

Acknowledgements absorption properties of chemically modified halloysite samples with X-ray

fluorescence and X-ray powder diffraction methods, Radiat. Phys. Chem. 93
(2013) 129–134.
The equipment was purchased thanks to the financial support [10] A. Kubala-Kukuś, M. Ludwikowska-Ke ß dzia, D. Banaś, J. Braziewicz, U.
of the European Regional Development Fund in the framework of Majewska, M. Pajek, J. Wudarczyk-Moćko, Application of the X-ray
fluorescence analysis and X-ray diffraction in geochemical studies of the
the Polish Innovative Economy Operational Program (contract
Pleistocene tills from Holy Cross Mountains, Radiat. Phys. Chem. 93 (2013) 92–
No. WNP-POIG.02.02.00–26-023/08). 98.
[11] J.L. (Ian) Campbell, Keynote talk: XRF and PIXE on the Mars Science Lab
Curiosity Rover, invited talk at EXRS 2014, 15-20 June 2014, Bologna, Italy.
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