Applied Clay Science 180 (2019) 105201

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Applied Clay Science

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

Research paper

A fast method for the chemical analysis of clays by total-reflection x-ray T

fluorescence spectroscopy (TXRF)
Ignazio Allegrettaa, , Biancamaria Ciascab, Maria D.R. Pizzigalloa, Veronica M.T. Lattanziob,
⁎

Roberto Terzanoa
a
Dipartimento di Scienze del Suolo, della Pianta e degli Alimenti, Università di Bari “Aldo Moro”, Via G. Amendola 165/A, 70126 Bari, Italy
b
Istituto di Scienze delle Produzioni Alimentari, Consiglio Nazionale delle Ricerche, via Amendola 122/O, 70126 Bari, Italy

ARTICLE INFO ABSTRACT

Keywords: A new, fast and cheap method for the analysis of clays using total-reflection x-ray fluorescence spectroscopy
TXRF (TXRF) has been developed following a full factorial experimental design to optimize the sample preparation
Clays conditions. The optimized method consists of the dispersion of 50 mg of clay into 2.5 ml of 1% Triton X-100
Elemental analysis solution, the deposition of 5 μl of the suspension onto a siliconized quartz reflector and drying it at 50 °C on a
Method development
heating plate. By using a commercial benchtop instrument, 15 major and trace elements were correctly quan-
tified with 1000 s live time acquisitions. Thirty minutes were sufficient for both sample preparation and analysis.
Validation experiments, performed using a certified reference material, showed recoveries in the range 80–120%
for the main targeted elements, whereas the within laboratory reproducibility (RSDWLR) and the repeatability
(RSDr) were lower than 20%, demonstrating the good precision and reliability of the method. Only in the case of
Si, the RSDWLR and RSDr were higher than 20%, due to the variable contribution of the quartz reflector. Suitable
LOD and LOQ values were estimated, varying from 0.1–0.4% for Al to 1–2 mg/kg for Sr, with higher sensitivity
for elements with higher fluorescence energy (and high atomic number, Z).
Finally, a good agreement was obtained between the results of the analysis of reference materials performed
with the new TXRF method and a reference method, such as wavelength dispersive x-ray fluorescence spec-
troscopy (WDXRF).
Based on the above performances, this method may represent a valuable and reliable alternative analytical
tool when only small amounts of clay samples are available such as in the case of mineral synthesis, clays
extraction from soils and sorption tests.

1. Introduction AES or ICP-MS analysis is very complex and time-consuming. In fact, it

Clays and clay minerals are widespread natural materials whose
characterization is needed in several research (e.g., geology, environ-
mental sciences, archaeometry, material science, soil science, etc.) and
industrial fields (e.g., ceramic and composite production, food proces-
sing, mining, pharmacy, etc.). Together with mineralogical and phy-
sical investigations, chemical analysis of clay samples is a crucial step in
their study and characterization. Several methods are available for the
chemical analysis of clays and aluminosilicates. The most common ones
require the use of analytical instruments based on inductively coupled
plasma sources associated to atomic emission spectrometers (ICP-AES)
or mass spectrometers (ICP-MS) (Gutsuz et al., 2017; Ndzana et al.,
2018). According to standard analytical methods (UNI ISO 21587-
1:2007 and UNI ISO 21587-3:2007), the sample preparation for ICP-
consists of several steps, including fusion, dehydration (or fusion and
coagulation), and sample decomposition. Hazardous chemicals (i.e.,
strong acids) and very expensive tools (e.g., platinum crucibles) are also
required. Furthermore, in some applications such as clays micro-
syntheses or sorption tests, the amount of sample necessary to accom-
plish the standard methods is often too large (1.2 g per replicate).
Gutsuz et al. (2017) have developed a method that requires only
200 mg of sample for the production of beads, which are then dissolved
in HNO3 for ICP-MS analysis. However, also in this case, the sample
preparation required several steps, and the thermal treatment (at
1050 °C) may cause the loss by volatilization of elements such as As, Hg
and Se. Neutron activation analysis (NAA) is another analytical tech-
nique used for the elemental characterization of clays. Even if the
amount of sample required for NAA is very small (80–130 mg) and no

⁎
Corresponding author.
E-mail address: ignazio.allegretta@uniba.it (I. Allegretta).

https://doi.org/10.1016/j.clay.2019.105201
Received 7 December 2018; Received in revised form 18 June 2019; Accepted 24 June 2019
0169-1317/ © 2019 Elsevier B.V. All rights reserved.
I. Allegretta, et al.
sample preparation is needed, the analysis can last several days, de-
pending on the radionuclide lifetime (Hein et al., 2002, 2004). X-ray
based spectroscopies are also widely used for the chemical analysis of
clays. Among them, wavelength dispersive x-ray fluorescence (WDXRF)
spectroscopy is the most common and diffuse (Allegretta et al., 2017a;
D'Elia et al., 2018; Hein et al., 2002, 2004; Lorentz et al., 2018;
Ogundiran and Kumar, 2015). For this kind of analysis, samples can be
prepared as pressed pellets or fused beads. In the first case, 1–5 g of
samples are ground and mixed with a binding agent and then pressed.
In this way, the sample preparation is very fast, but the large amount of
sample needed remains a critical issue. On the other side, when pre-
paring fused beads, 300 mg of sample are mixed with a fusing agent
(usually lithium borate) and then poured in platinum crucibles for
thermal treatment (800–1000 °C), resulting however in a much longer
sample preparation procedure (Margui et al., 2016). In the field of x-ray
based techniques, total-reflection x-ray fluorescence spectroscopy
(TXRF) is a very good method for the analysis of small amounts of
sample (20–100 mg), requiring a very simple and fast sample pre-
paration procedure. The possibility to perform direct analysis with
limited sample treatment makes this technique suitable for the chemical
characterization of several kinds of environmental and geological
samples (Klockenkämper and von Bohlen, 2015). Gerowinski and Goetz
(1987) analysed major, minor and trace elements in different soil re-
ference materials using TXRF on acid digested samples. Towett et al.
(2013, 2015) investigated soil samples without preliminary digestion,
using slurries, resulting in a much faster sample preparation. In only
few cases, the elemental composition of rocks and aluminosilicate
materials was determined by TXRF (Cherkashina et al., 2013, 2014). In
these cases, only few elements were quantified and no specific study
was carried out to set up the most suitable analytical parameters for the
TXRF analysis. The problem of sample pretreatment for TXRF analysis
of aluminosilicates was first faced by García-Heras et al. (1997), who
focused their attention on specimen grinding and dispersant medium.
This is the only case in which a clay sample was analysed by TXRF, even
if the clay reference material was analysed only to validate a method for
ceramic characterization. To our knowledge, no TXRF method has been
developed for the analysis of clays. In particular, such a method could
be advantageous when the amount of sample is scarce (e.g., deriving
from clay extractions from soils, microsyntheses, sorption tests, etc.) or
not sufficient for the application of other methodologies.
For this reason, the present work aims at setting up a fast and robust
analytical method for the direct analysis of clays using TXRF spectro-
scopy. To this purpose, samples were analysed as slurries and a full
factorial experimental design was used to determine the best sample
preparation procedure. The method was optimized and validated em-
ploying two standard certified reference clay materials and TXRF re-
sults were compared with those obtained by WDXRF, used as reference
analytical method.
2. Basics of total-reflection X-ray fluorescence
Generally, in X-ray fluorescence spectroscopy (XRF), a primary x-
ray beam (generated by the bombardment of an anode with accelerated
electrons) is focused on a sample. The interaction between the primary
beam and the elements constituting the sample generates a secondary x-
ray radiation which is characterized by different emission lines (K, L
and M lines). These lines are characteristic of each chemical element
and are produced by the removal of a bound inner electron, exited by
the primary beam, which is then replaced by an outer bound electron. A
background signal is also present in the secondary radiation. It is pro-
duced by the inelastic scattering of the primary beam continuous
spectrum (also called bremsstrahlung) (Beckhoff et al., 2006).
TXRF is a special type of x-ray fluorescence spectroscopy (XRF).
Differently from traditional XRF (where the incidence angle of the
primary x-ray beam to the sample is about 45°), the x-ray beam im-
pinges the sample at an angle lower than a critical angle (< 1°). The
2
Applied Clay Science 180 (2019) 105201
critical angle depends on the material of the sample carrier and the
energy of the incident beam. When this condition is satisfied, the in-
cident beam does not refract into the sample carrier but is totally re-
flected, producing several advantages for XRF analyses: i) reduction of
matrix absorption effects, ii) increase of the signal-to-noise (S/N) ratio,
and iii) consequent improvement of the detection limit (in the range of
mg/kg for solids and μg/l or lower in the case of liquids). However, to
achieve these results, a monochromatic x-ray beam is required. For this
reason, TXRF spectrometers are commonly equipped with a filter, a
reflector and a series of slits that cut off the bremsstrahlung and focalize
the monochromatic beam onto a second reflector (the sample carrier),
where the sample is deposited. The versatility of the technique allows to
analyse several kinds of materials, such as liquids (Borgese et al., 2018),
gases (Böttger et al., 2018), biological samples (Allegretta et al., 2017b;
Markert et al., 1994), vegetables (Allegretta et al., 2019; Paradiso et al.,
2018), nanomaterials (Bahadir et al., 2018), soils (Towett et al., 2013,
2015), minerals (Cherkashina et al., 2013, 2014), composites (García-
Heras et al., 1997, 2001), etc. For solid samples, small specimens can be
directly analysed by suspending the powdered material in a liquid
dispersant agent where an internal standard is added. Then, a small
volume (few microliters) of the suspension is deposited on a sample
carrier (reflector) and the liquid completely evaporated before the
analysis. Further information on the physics, instrumentation and per-
formances of TXRF are available in Klockenkämper and von Bohlen
(2015).
3. Materials and methods
3.1. Experimental design
3.1.1. Optimization of the analytical procedure
A set of eight aluminosilicate reference materials (GS-N, UB-N, BE-
N, AC-E, PM-S, DR-N, WS-E and AN-G, SARM-CRPG, France) were used
to test the linearity of the instrument response and to calibrate the
element relative sensitivities (Sr). For this step, Se was used as internal
standard and its Sr was set equal to 1.
A chemometric approach was used to optimize the conditions for
the elemental analysis of clays in order to obtain maximum recovery
rates. For this purpose, a full factorial design was generated using the
software package MINITAB™ Statistical Software for Windows, version
14 (Minitab, State College, PA, USA). A phlogopite reference material
(Mica-Mg by SARM-CRPG, France) was employed. Three independent
factors were tested: sample weight (A), dispersant volume (B) and re-
flector type (C), in order to get information about the effect of these
three factors and their interactions on the recovery. Each factor (A, B
and C) was set at two levels (low and high, see Table 1). The effect to be
observed was the change in recovery rates when switching each factor
from one level to the other. In addition, two centre points were also
considered (Table 1), to determine the analytical error in this series of
experiments. Calculated error was then used to check whether the ef-
fects and the interactions were significant or not. A total of 20 experi-
ments were conducted in a randomized order. At the end, for the op-
timization, the following ten sample preparations were done:
Table 1
Parameters and their levels considered in the experimental design for the op-
timization of the method.
Variables Levels
Low Centre point High
Sample weight (mg) 50 75 100
Dispersant volume (ml) 2.5 3.75 5
Reflector Quartz Plexiglas
I. Allegretta, et al.
• 50 mg of clay in 2.5 ml of Triton X-100, deposited on quartz re-
flector;
• 50 mg of clay in 2.5 ml of Triton X-100, deposited on plexiglas re-
flector;
• 50 mg of clay in 5 ml of Triton X-100, deposited on quartz reflector;
• 50 mg of clay in 5 ml of Triton X-100, deposited on plexiglas re-
flector;
• 75 mg of clay in 3.75 ml of Triton X-100, deposited on quartz re-
flector;
• 75 mg of clay in 3.75 ml of Triton X-100, deposited on plexiglas
reflector;
• 100 mg of clay in 2.5 ml of Triton X-100, deposited on quartz re-
flector;
• 100 mg of clay in 2.5 ml of Triton X-100, deposited on plexiglas
reflector;
• 100 mg of clay in 5 ml of Triton X-100, deposited on quartz reflector;
• 100 mg of clay in 5 ml of Triton X-100, deposited on plexiglas re-
flector.
3.1.2. Validation design
The optimized TXRF method was validated using a zinnwaldite re-
ference material (ZW-C by SARM-CRPG, France).
The validation experiments were carried out according to a 2-day
nested design. According to the experimental design, 5 independent
analyses were carried out on each day. In addition, three instrumental
replicates for each sample were measured, resulting in 30 measure-
ments in total.
The analytical results, expressed as mg/kg, were then subjected to
analysis of variance (ANOVA) as specified by ISO 5725-3 (1994).
The model that underlies the analysis of variance of the data col-
lected following this fully nested design is expressed by the following
equation:
Yijk = TV + Di + Sij + Rijk
where Yijk is the value of the single measurement, TV is the true value,
Di is the between-day variability (days number from 1 to i), Sij is the
between-sample preparation variability (replicated sample preparations
number from 1 to j) and Rijk is the variability associated to the instru-
mental analysis (instrumental replicate number from 1 to k). The sum of
the last two factors (instrumental analysis and between-sample pre-
paration variability) gives the precision under repeatability conditions,
whereas the sum of all components (including the between-day varia-
bility) gives the within laboratory reproducibility. The precision is ex-
pressed in terms of relative standard deviation of repeatability (RSDr)
and relative standard deviation of within laboratory reproducibility
(RSDWLR). The trueness of the method was evaluated via the analysis of
ZW-C reference material as closeness of agreement between the value
obtained from the optimized TXRF method and the certified reference
concentrations and expressed as recovery. Limit of detection (LOD) and
limit of quantification (LOQ) were also assessed according to
Klockenkämper and von Bohlen (2015).
3.2. TXRF analysis
Clay samples were finely ground for 2 min with a vibromilling
system (MM400, Retsch, Germany), weighed in a 10 ml polypropylene
tube and suspended in a 1% Triton X-100 (Sigma Aldrich CHEMIE
GmbH, Germany) solution, used as dispersant agent. After slurry pre-
paration, 10 μl of Se 1000 mg/l standard solution (Sigma Aldrich
CHEMIE GmbH, Germany) were added to the suspension. The suspen-
sion was vortexed for 30 s and then placed in an ultrasonic bath for
10 min. After vortexing again for 30 s, 5 μl of suspension were pipetted
onto a reflector (made of quartz or plexiglas) under a laminar flow
hood. The deposited drop was left drying on a heating plate at 50 °C for
5–10 min. After drying, the reflector was loaded on a reflector holder
and analysed.
3
Applied Clay Science 180 (2019) 105201
TXRF analyses were carried out using a benchtop S2 Picofox (Bruker
Nano GmbH, Germany) spectrometer at environmental pressure. The
instrument was equipped with a Mo microfocus tube working at 50 kV
and 600 μA, a multilayer monochromator and an XFlash® silicon drift
detector with 30 mm2 active area and an energy resolution lower than
150 eV at Mn-Kα. All samples were analysed for 1000 s live time, as
suggested by Towett et al. (2013).
3.3. WDXRF analyses
For WDXRF analyses, 5.0 g of powdered clay were mixed with 2 ml
of 2% (w/v) solution of Elvacite® 2046 (PANalytical B.V., The
Netherlands) in RPE grade acetone (Carlo Erba Reagenti Spa, Italy).
After acetone evaporation, the powder was poured into an aluminium
cup where 5.0 g of RPE grade boric acid (Carlo Erba Reagenti Spa, Italy)
were previously weighed. Then, the sample was pressed at 25 t for
5 min, in order to obtain a flat and uniform disk. Sample analysis was
carried out using a Supermini200 WDXRF spectrometer (Rigaku
Corporation, Japan) equipped with a Pd source (200 W, 50 kV, 4 mA), a
Zr filter, and three interchangeable crystals (LiF, PET and RX25) which
focus the secondary beam on a proportional counter or a scintillator
detector. Analysis were performed under vacuum (< 12 Pa). The in-
strument was calibrated using a set of 16 aluminosilicate reference
materials by SARM-CRPG (France).
3.4. Optical and electron microscopy observations
Optical and electron microscopies were used to evaluate the quality
of sample deposition on the reflector. In particular, an SZH10 stereo-
microscope (Olympus Optical Co. GmbH, Germany) equipped with
optical fibre illumination was used to study the shape of the deposition
on both quartz and plexiglas reflectors. A field emission gun scanning
electron microscope (FEG-SEM) Zeiss Σigma 300 VP (Zeiss, Germany),
equipped with a secondary electron detector, was used for the de-
termination of the thickness of the deposition. In particular, 5 μl of
suspension were pipetted onto the reflectors (near the border and not at
the centre). Then, the reflectors were fixed from their lateral side onto
aluminium stubs. In order to ensure the electron conductivity, copper
connections were created between the reflector and the stub and, fi-
nally, the sample was carbon coated. In this way, the electron beam
impinged on the sample horizontally ad a transversal view of the de-
position could be acquired. FEG-SEM analyses were carried out at
5–15 kV with 7.5 mm working distance. For the determination of the
clay grain size, 10 mg of the clay material were suspended into 100 ml
of distilled water. After vortexing, 100 μl were pipetted onto an alu-
minium stub covered by a carbon tape and after drying at room tem-
perature it was carbon coated. An area of 1.0 × 1.4 mm, corresponding
to the central part of the stub, was observed using the secondary
electron detector. The image was then processed using AZtecFeature
software (Oxford Instruments, United Kingdom) in order to determine
the average size of about 1300 identified particles.
4. Results and discussion
For TXRF analyses, the quality of sample deposition on the sample
carrier is extremely important to obtain good quantitative data. In
particular, the deposition of a thin-film of material characterized by
very fine particles is fundamental. According to García-Heras et al.
(1997), a grain size of 10 μm is suitable to get reliable quantitative
TXRF data for aluminosilicate materials. As shown in Fig. 1, the grain
size of both Mica-Mg and ZW-C reference materials analysed was lower
than 10 μm, for most of the particles. In particular, for Mica-Mg
(Fig. 1A), the average grain size was 4.6 μm with 92% of the particles
having a size < 10 μm. In the case of ZW-C (Fig. 1B), the average grain
size was 5.6 μm, and 84% of the particles had a grain size < 10 μm. In
both cases, the features classified as larger than 10 μm were mostly
I. Allegretta, et al. Applied Clay Science 180 (2019) 105201

Table 2
Fluorescence line used for the element detection and the calculated relative
sensitivities (Sr).
Element Fluorescence Line Energy (keV) Sr

Mg Kα 1.125 0.000153
Al Kα 1.486 0.000595
Si Kα 1.740 0.002285
Cl Kα 2.622 0.014477
K Kα 3.314 0.037427
Ca Kα 3.692 0.083714
Ti Kα 4.512 0.142429
V Kα 4.953 0.177963
Cr Kα 5.415 0.230296
Mn Kα 5.900 0.280364
Fe Kα 6.405 0.355982
Ni Kα 7.480 0.517312
Cu Kα 8.046 0.581101
Zn Kα 8.637 0.675427
Ga Kα 9.251 0.775121
Se Kα 11.224 1.000000
Rb Kα 13.396 1.163880
Sr Kα 14.165 1.166584
Ba Lα 4.466 0.064744
Pb Lα 10.551 0.674929
Fig. 1. Particle grain size in terms of equivalent circular diameter (ECD) of
Mica-Mg (A) and ZW-C (B) after image analysis of FEG-SEM micrograph.

aggregates of two or more particles having individually a grain size A

lower than 10 μm. For this reason, the grain size of both samples could
be considered suitable for the preparation of suspensions for TXRF
analyses. For most of the clays, this prerequisite can be considered
easily achievable for the intrinsic characteristics of these materials.
Another parameter to monitor is the thickness of the dried deposition.
In order to avoid the mass adsorption effect of the sample, the thickness
of the deposition should be lower than a critical thickness (tcrit). Ac-
cording to Klockenkämper and von Bohlen (2015), tcrit ≈ 50 nm for 2 mm
mineral powders. However, the particle size of both Mica-Mg and ZW-C
did not allow to achieve such a thin deposition and therefore mass
adsorption effects cannot be neglected. For this reason, the relative B
TXRF sensitivity (Sr) of each element was preliminarily calibrated using
eight aluminosilicate reference materials (GS-N, UB-N, BE-N, AC-E, PM-
S, DR-N, WS-E and AN-G, SARM-CRPG, France) prepared in the same
way as the samples. Selenium internal standard was used for the re-
lative sensitivity calibration and the Sr of Se was considered equal to 1.
This operation was done after testing the linearity of the response be-
tween the fluorescence intensity and the real concentration of the ele-
ment in the aluminosilicate reference materials (Fig. S1). Since Si and S
2 mm
were also present in quartz and plexiglas reflectors, respectively, their
relative sensitivity was obtained by interpolating the relative sensitiv-
ities of the other elements with a fifth-degree polynomial function. The
values of Sr calculated for each specific element line are reported in
C
Table 2.
In order to reduce the size of the sample dispersion on the reflector
surface, usually hydrophobization of the sample carrier with a silico-
nizing agent is needed. While for quartz carriers this is a common
practice (Cherkashina et al., 2013, 2014; Towett et al., 2013, 2015), for
plexiglas reflectors no indications are reported in the literature. The
siliconizing agent (silicon solution, SERVA, Germany) allowed to obtain
a less dispersed dried deposition on plexiglas reflectors (Fig. 2A and B), 2 mm
even if the deposition on the quartz reflectors was more regular and
uniform (Fig. 2C).
Fig. 2. Dried deposition of clay on a non‑siliconized plexiglas reflector (A), a
siliconized plexiglas reflector (B) and a siliconized quartz reflector (C).

4.1. Optimization
For the method optimization, the Mica-Mg reference material was
employed and its TXRF spectrum is reported in Fig. 3. The K-lines of
major (Mg, Al, Si, K, Ca, Ti, Mn and Fe) and minor (Cl, V, Cr, Ni, Cu, Zn,
Ga, Rb and Sr) elements and the L-lines of Ba and Pb were clearly
detected in the spectrum. Since TXRF analyses were carried out in air at
atmospheric pressure, a weak peak of Ar was also visible in the spec-
trum. Because of atmospheric Ar, Na, an important major element in
clays, cannot be detected by TXRF, since its fluorescence lines are ab-
sorbed by Ar atoms. Prost et al. (2018) and Streli et al. (2004)

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I. Allegretta, et al. Applied Clay Science 180 (2019) 105201

A B

Ca- Kα
K - Kα
Mg Ca Fe Ni Cu Ga Pb Se Rb Sr

K - Kβ
Al K Ti Mn Zn
Si Ba Cr
log I (cps)

log I (cps)
. . . . . .
E (keV) E (keV)

Fig. 3. TXRF spectra of the clay reference material Mica-Mg prepared using 50 mg of sample, 2.5 ml of Triton solution and deposited on a quartz (black) and plexiglas
(red) reflectors (A). The magnification of the spectra in the range 3.0–4.0 keV, shows the overlapping of the K-Kβ and Ca-Kα lines (B). (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this article.)

demonstrated that analysing samples under vacuum and using a low
energy source could overcome this problem, allowing the detection of
light elements (also with atomic numbers lower than Na).
The experimental design matrix and the recoveries obtained in each
condition are shown in Table 3. According to these results, the highest
number of elements which was possible to quantify with a good accu-
racy was achieved for samples prepared using 50 mg of material dis-
persed into 2.5 ml Triton solution and deposited onto quartz reflectors.
In fact, with this sample preparation, 15 different elements (on 19 de-
tected elements) were quantified with a recovery in the range
80–120%. Among these elements, all major elements (except for Ca)
and trace elements (Cl, Ni, Cu, Zn, Ga, Rb, Sr and Pb) were correctly
quantified. Calcium was not correctly quantified because the intense
potassium K-β signal overlaps with the very weak calcium K-α peak
(Fig. 3B), thus biasing its correct quantification. Good results were also
obtained with 75 mg of sample, 3.75 ml of dispersant agent and using
quartz reflectors (13 elements correctly quantified), even if an im-
portant major element, Mg, was not correctly quantified. When plex-
iglas was used as reflector, accurate data were obtained using 50 mg of
sample into 5 ml of dispersant or 100 mg into 2.5 ml (12 elements).
However, in these cases, major elements concentrations strongly dif-
fered from reference values.
Statistical significance of the experimental factors contributions,
and their first-order interactions, were determined by analysis of var-
iance (ANOVA). The estimated standardized effects on the recovery of
some relevant elements (Mg, Si, K, Fe, Sr and Ba) are summarized in
Fig. 4. These elements were chosen because their characteristic fluor-
escence signals (K-lines for Mg, Si, K, Fe, Sr and L-lines for Ba) cover all
the energy ranges comprised in the spectrum of the detected elements.
The red dotted line is calculated from the random error obtained from

Table 3
Recovery (%) obtained for each element after the preparation of slurries using different parameters and TXRF analysis. A recovery of 80–120% was considered
acceptable for the correct element detection. The certified concentration of each element is also reported.
Sample weight (mg) 50 50 50 50 75 75 100 100 100 100 Reference Value

Triton solution volume (ml) 2.5 2.5 5 5 3.75 3.75 2.5 2.5 5 5

Reflector Quartz Plexiglas Quartz Plexiglas Quartz Plexiglas Quartz Plexiglas Quartz Plexiglas mg/kg
Mg 111 222 132 214 131 246 51 172 110 236 12.30 (%)
Al 102 185 123 192 115 204 49 137 98 194 8.04 (%)
Si 85 126 123 127 100 139 42 92 86 132 17.89 (%)
Cl 100 179 132 169 110 200 59 118 97 184 800
K 107 149 117 132 112 154 74 118 94 142 8.25 (%)
Ca 36 42 36 27 42 42 37 34 30 40 0.06 (%)
Ti 84 112 87 95 87 114 64 90 71 104 0.98 (%)
V 133 185 145 106 156 167 163 137 105 170 90
Cr 65 110 64 99 56 82 46 90 64 76 100
Mn 82 105 82 87 84 105 67 87 68 95 0.20 (%)
Fe 92 116 90 97 93 116 76 97 76 105 6.62 (%)
Ni 96 122 94 104 96 119 79 100 80 108 110
Cu 86 46 21 39 17 28 32 23 39 24 4
Zn 104 126 97 104 101 126 86 108 83 112 290
Ga 86 111 84 94 86 110 72 92 71 101 21
Rb 105 128 98 104 103 127 91 110 85 113 1300
Sr 113 126 103 106 108 119 96 112 89 107 27
Ba 75 92 71 81 72 91 54 79 63 81 4000
Pb 109 159 86 94 117 181 112 123 83 129 9
Total number of elements with a recovery in the range 80–120% 15 6 10 12 13 7 4 12 11 9

5
I. Allegretta, et al. Applied Clay Science 180 (2019) 105201

Mg Si K
2.20 2.20 2.20

C C C
B B A
A A AB
AB AC B
AC AB AC
ABC BC ABC
BC ABC BC
0 5 10 15 20 0 2 4 6 8 10 12 14 0 2 4 6 8 10

Fe Sr Ba
2.20 2.20 2.20

C C C

A A A

AB B AB

ABC AC AC

AC AB BC

B ABC B

BC BC ABC

0.0 0.5 1.0 1.5 2.0 2.5 0 1 2 3 4 5 6

0 1 2 3 4 5 6

A = sample weight B = dispersant volume C = reflector

Fig. 4. Pareto charts of Mg, Si, K, Fe, Sr and Ba showing the contribution of the sample weight (A), dispersant volume (B), reflector (C) and their combination (AB,
AC, BC, ABC) for the quantification of the quantification of the elements.

the replicates of the experiments having all factors at the centre level.
The bars overcoming the red dotted line represent the factors (single
variables and their combinations) which significantly affect the element
quantification. Generally, with the increase of the element character-
istic K fluorescence energy (i.e. increase of Z), the number of factors
affecting the quantification of the element concentration is reduced. In
fact, for elements quantified using K-α lines (e.g., Mg, Si, K, Fe and Sr,
Fig. 4) the number of factors influencing the quantification changes
from 5 (for low Z elements like Mg) to 1 (for high Z elements like Sr).
However, for elements quantified using L-lines (e.g., Ba, Fig. 4), which
have a higher Z than Sr and Fe, the number of factors which affected
their quantification increases again to 2.
Among all the studied factors, the material of the reflector (C) was
the variable which mostly affected the recovery of the elements. This
could be explained since quartz and plexiglas have two different critical
angles of 0.10° and 0.076°, respectively (Klockenkämper and von
Bohlen, 2015). Since in commercial TXRF spetrometers the incident
beam is set at a fixed angle (usually at the quartz critical angle), other
types of reflectors, like plexiglas ones, can suffer for a not perfect
geometry thus giving slightly biased results (Table 3). The second
variable which affected the correct element quantification was the
sample weight (A). In particular, the higher the amount of suspended
sample, the thicker is the deposition layer, with a consequent reduction
of the total reflection effect due to matrix absorption attenuation. In
fact, both the primary beam and the reflected beam should pass through
and emerge from the sample layer with a consequent x-ray attenuation,
mainly due to photoelectric adsorption (Klockenkämper and von
Bohlen, 2015). The effect of the dispersant volume (B) on the quantified
values was very low with the exception of Mg and Si, for which it was
comparable to that of the sample weight. An important factor influen-
cing data quantification was the combination of the two variables A and
B (AB), in particular for the elements with lower energy fluorescence
emissions (from Mg to Ti). This highlights the importance of the con-
centration of sample particles suspended in the dispersant agent, which
affects the thickness and the distribution of the deposition layer on the
reflector. In fact, considering only the tests where quartz reflectors were
employed, the best performances for both major and trace elements
were obtained when the ratio between sample weight and solution
volume (A/B) was equal to 20 mg/ml (Table 3). When the ratio was
higher than 20 mg/ml (e.g., 100 mg in 2.5 ml), the thickness of the
deposition increased to a size that reduced the total reflection effect
(Fig. 5), causing a higher matrix absorption of the fluorescence signal
and the consequent underestimation of almost all elements (Table 3).
On the contrary, when the sample was too much diluted in the dis-
persant agent (i.e. 50 mg into 5 ml), a slight overestimation of the light
elements was observed (Table 3).
In the case of Si, all the variables and their interactions (AB, AC, BC
and ABC) affected its quantification, suggesting that a right balance
among the three variables needs to be found for its correct analysis.
Quartz reflectors are made of SiO2 and, for this reason, the thickness of
the sample deposition layer also influences the fluorescence signal of
the Si of the reflector. In fact, when A/B was < 20 mg/ml, less material
was deposited onto the reflector, thus increasing the reflector con-
tribution to the silicon K-α signal and causing an overestimation of Si in
the sample. Similarly to what happens for the other elements, when A/B
was > 20 mg/ml, the higher thickness of the deposition caused a larger
matrix absorption and thus an underestimation of Si.
Since the best results were achieved suspending 50 mg of clay into
2.5 ml of Triton X-100 solution and using quartz as sample carrier, this
procedure was identified as the optimized method and was, therefore,
subjected to a validation process.
4.2. Validation
The optimized method was subjected to intra-laboratory validation
using Zinnwaldite reference material (ZW-C) as test material.
According to the optimized protocol, 50 mg of sample were sus-
pended in 2.5 ml of Triton solution, followed by the deposition of 5 μl of
suspension on quartz reflectors. A typical TXRF spectrum of ZW-C is
shown in Fig. 6. The detected elements were Al, Si, K, Ca, Ti, Cr, Mn, Fe,

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I. Allegretta, et al. Applied Clay Science 180 (2019) 105201

A B

Fig. 5. Secondary electron FEG-SEM micrographs showing the thickness of the clay deposition onto a quartz reflector of a suspension made with 2.5 ml of dispersant
agent, 50 mg (A) and 100 mg of sample (B).

Ca Fe Ni Cu Ga Pb Se Rb Sr reference values (11 ± 16.87 mg/kg for Ni and 82 ± 23.75 mg/kg for
Al K Mn Zn Pb, Govindaraju et al., 1994). Regarding to aluminium, its K-α peak
Si Ti Cr overlapped with the L-lines of rubidium, whose intensity was one order
of magnitude higher than in the case of the Mica-Mg reference material.
This, in addition to the presence of the potassium escape peak
(1.574 keV), could lead to an incorrect deconvolution of the aluminium
K-α fluorescence peak, thus causing an overestimation of this element.
log I (cps)

In Table 4, the data of the within laboratory reproducibility

E (keV)
Fig. 6. TXRF spectrum of ZW-C reference material.
Ni, Cu, Zn, Ga, Rb, Sr and Pb. The fluorescence lines of atmospheric Ar,
the source (Mo) and the internal standard (Se) were also observed.
The results of the validation process are shown in Table 4. With the
exception of Al, Ni and Pb, all the elements had a recovery in the range
80–120% demonstrating the good accuracy of the method. The over-
estimation of Ni and Pb with respect to the reference values could be
imputed to an uneven distribution of these elements in the test sample,
as suggested by the high standard deviations associated with the
(RSDWLR) and repeatability (RSDr) are also reported. As mentioned
before, RSDWLR takes into account the contribution of three sources of
variability (day, sample preparation and instrumental analysis) while
RSDr includes the variability associated to sample preparation and in-
strumental analysis. The highest RSDWLR was obtained for Cr, Ni and Si
for which it exceeded 20%. However, while for Cr and Ni this could be
explained by the high variability of these elements in the reference
material (see Govindaraju et al., 1994), for Si the high RSDWLR could be
imputed to the contribution of the quartz reflector. Despite the con-
tribution of the reflector, the overall method precision was considered
fit-for-the purpose of clay analysis. Regarding RSDr, it followed the
same trend of RSDWLR and for some elements (Si, K, Ca, Ti, Mn, Fe, Zn,
Ga, Rb and Sr) it was even lower, testifying the good precision of the
method. The contributions given by the analytical replicates (Instru-
ment), sample preparation (Sample) and the day of the analysis (Day)
were different and depended on the element. However, the different
contributions were irrelevant due to the very low RSDr, which testified
a satisfactory repeatability and precision of the method.
Finally, the limit of detection (LOD) and quantification (LOQ) were
also determined according to Klockenkämper and von Bohlen (2015):

Table 4
Results of the validation performed on the ZW-C reference material. The reference value (RV), the determined concentration (Mean), the recovery, the within
laboratory reproducibility (RSDWLR), the repeatability (RSDr) with its different contributions (Day, Sample and Instrument), the limits of detection (LOD) and
quantification (LOQ) are reported for each element.
Elements

Al Si K Ca Ti Cr Mn Fe Ni Cu Zn Ga Rb Sr Pb

RV (mg/kg) 97,600 252,200 63,600 2600 300 56 7500 66,200 11 39 1050 99 8500 17 80
Mean (mg/kg) 131,938 247,412 65,803 2264 270 63 6175 55,359 14 26 1052 81 7734 18 126
Recovery (%) 135 98 103 87 90 112 82 84 127 68 100 82 91 108 158
RSDWLR (%) 5 24 7 11 9 95 12 10 37 12 11 10 11 15 18
RSDr (%) 5 21 4 5 6 95 6 6 37 12 7 5 6 10 18
Day 0 21 65 79 52 0 77 66 0 2 63 68 69 58 0
Sample 19 8 9 9 28 95 13 21 1 26 21 21 20 28 0
Instrument 81 71 26 12 20 5 10 13 99 71 16 11 11 14 100
LOD (mg/kg) 1153 279 24 8 5 4 4 4 1 1 1 1 1 1 1
LOQ (mg/kg) 3845 930 81 25 17 12 14 12 3 3 3 2 3 2 2

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I. Allegretta, et al. Applied Clay Science 180 (2019) 105201

A B
TXRF TXRF
WDXRF WDXRF
Recovery (%)

Recovery (%)
Fig. 7. Comparison of TXRF and WDXRF results obtained on Mica-Mg (A) and ZW-C (B) reference materials.

LOD = 3
Ci
2Nback
Nnet
Ci
LOQ = 10 2Nback
Nnet
where Ci, Nnet and Nback are the concentration of the analysed element,
the net area of the peak of the analysed element and the background
count rate, respectively. Both LOD and LOQ decreased with the increase
of the element atomic number (Table 4). LOD varied from 1153 mg/kg
for Al to < 1 mg/kg for Sr. In the case of LOQ, it ranged from 3845 mg/
kg for Al to 2 mg/kg for Ga, Sr, and Pb. These values confirm that this
method is suitable for the characterization and study of clays, where
elements concentration are usually higher than the LOQs calculated for
each element.
4.3. Comparison with WDXRF
TXRF results on both ZW-C and Mica-Mg were compared with the
data obtained by WDXRF, used as reference analytical method (Fig. 7
and Table 5). In fact, WDXRF is a widely used and worldwide re-
cognized method for clay analyses (Allegretta et al., 2017a; D'Elia et al.,
2018; Hein et al., 2002, 2004; Lorentz et al., 2018; Ogundiran and
Kumar, 2015). The comparison was done on major elements, since they
are the most important for clay characterization, in particular to sup-
port XRD mineralogical analyses (Omotoso et al., 2006; Ottner et al.,
2000). Results showed that almost all elements were in the range
80–120% of recovery for both techniques. Excluding potassium, TXRF
data were more dispersed than WDXRF ones. This is due to the larger
amount of sample used in WDXRF analyses (5 g) which allows to reduce
errors due to sample heterogeneity. Moreover, even if the majority of
the analysed samples had an average grain size lower than 10 μm
(Fig. 1), some aggregates could have formed during the deposition of
the sample on quartz reflectors, thus slightly modifying the response of
the sample to primary beam excitation and increasing data variability
in TXRF. This effect was more evident for Si analysis, where the com-
position of the quartz reflector contributed to the variability of Si
quantification. As expected, Na could be analysed only with WDXRF
since the analyses was performed under vacuum (Table 5). WDXRF was
less accurate than TXRF for the quantification of Mg in Mica-Mg re-
ference material (Fig. 7A). In the case of ZW-C (Fig. 7B), where Mg
concentration was lower (965 mg/kg), TXRF was not able to detect the
element, while WDXRF strongly underestimated it since it was close to
its LOQ (1050 mg/kg). Calcium in Mica-Mg was underestimated with
TXRF, while it was not detected at all with WDXRF, due to its very low
concentration and the overlapping with the strong potassium K-β
signal, which covered the calcium K-α peak. However, Fig. 7 clearly

Table 5
Certified concentration. TXRF and WDXRF results obtained on both Mica-Mg and ZW-C reference materials. Both the oxide concentration (Conc.) and the standard
deviation (σ) are expressed in weight percentage.
Element Mica-Mg ZW-C

Certified Value TXRF WDXRF Certified Value TXRF WDXRF

Conc. (%) σ (%) Conc. (%) σ (%) Conc. (%) σ (%) Conc. (%) σ (%) Conc. (%) σ (%) Conc. (%) σ (%)

SiO2 38.30 0.36 32.72 0.89 37.50 0.38 54.00 0.98 52.98 11.90 54.13 0.54
TiO2 1.63 0.10 1.37 0.02 1.74 0.02 0.05 0.02 0.03 0.00 0.05 0.00
Al2O3 15.20 0.44 15.56 1.09 12.50 0.15 18.45 0.66 24.93 1.27 19.20 0.18
Fe2O3 9.46 0.34 8.75 0.27 9.74 0.09 9.46 0.47 7.92 0.64 10.35 0.09
MnO 0.26 0.04 0.21 0.01 0.24 0.00 0.97 0.10 0.80 0.07 0.97 0.01
MgO 20.40 0.04 22.54 1.04 25.47 0.20 0.16 0.05 – – 0.08 0.00
CaO 0.08 0.04 0.03 0.00 – – 0.37 0.07 0.31 0.03 0.31 0.01
Na2O 0.12 0.21 – – 0.24 0.02 0.33 0.10 – – 0.47 0.05
K2O 10.00 0.29 10.67 0.04 10.24 0.70 7.72 0.41 7.98 0.43 7.90 0.54
Li2O 0.05 0.02 – – – – 4.85 0.80 – – – –
P2O5 0.01 0.27 – – – – 0.03 0.04 – – – –
F 2.85 0.11 – – – – 5.45 0.66 – – – –
LOIa 1.75b – – – – – 2.30b – – – – –

a
LOI: Loss on ignition.
b
proposed value.

8
I. Allegretta, et al.
shows that the two techniques give substantially the same information
regarding the average elemental composition of clays with good accu-
racy and different grades of precision, mostly depending on the element
and type of clay.
5. Conclusions
In the present study, a new fast method for the chemical char-
acterization of clays using TXRF was developed and discussed. The
method was optimized and validated using two certified reference
materials (phlogopite Mica-Mg and zinnwaldite ZW-C) and then com-
pared with a widely used and recognized method such as WDXRF. The
best sample preparation procedure consisted in dispersing 50 mg of clay
into 2.5 ml of 1% Triton X-100 solution, depositing 5 μl of the suspen-
sion onto a siliconized quartz reflector and drying it at 50 °C on a
heating plate. TXRF analysis was carried out for 1000 s live time with a
commercial benchtop instrument. In this way, 15 major, minor and
trace elements were correctly quantified. Sodium could not be de-
termined due to its very weak fluorescence signal that is absorbed by
atmospheric Ar. The within laboratory riproducibility and the repeat-
ability were lower than 20%, demonstrating the good precision and
reliability of the method. Only in the case of Si, the RSDWLR and RSDr
were higher than 20%, due to the variable contribution of the quartz
reflector. The LOD and LOQ are suitable for the application of the
method to the analysis of clays, varying from 0.1–0.4% for Al to
1–2 mg/kg for Sr, with higher sensitivity for elements with higher
fluorescence energy. TXRF results were similar to those of WDXRF,
suggesting the possibility to use of this technique instead of “more
traditional” ones.
The developed method was simple, fast, cheap and eco-friendly.
Moreover, since a small amount of sample is required, the method could
be applied especially to those fields of research in which a small
quantity of sample can be produced such as mineral synthesis, clays
extraction from soils, sorption tests, etc.
Further developments of the method should concern the im-
plementation of TXRF spectrometers with vacuum pump and/or low
energy tubes which may allow to detect also Na, which is an important
element for clay characterization. Based on the satisfactory results ob-
tained in the intra-laboratory validation study, the method proposed
herein can be considered for full inter-laboratory validation, in order to
evaluate its robusteness among different laboratories and propose a
standard reference protocol for the analysis of clay by TXRF.
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.clay.2019.105201.
Acknowledgments
TXRF analysis were performed at the “Micro X-ray Lab” of the
University of Bari (Italy) supported by Regione Puglia (Programma
Operativo Regione Puglia - FERS 2000–2006 -Risorse Liberate -
Obiettivo Convergenza).
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(Alternative to the X-ray Fluorescence Method) - Part 1: Apparatus, Reagents,
Dissolution and Gravimetric Silica.

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