Talanta 161 (2016) 359–367

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Talanta
journal homepage: www.elsevier.com/locate/talanta

Calibration of handheld X-ray fluorescence (XRF) equipment for

optimum determination of elemental concentrations in sediment
samples
K. Gabriela Mejía-Piña a, Miguel Angel Huerta-Diaz b,n, O. González-Yajimovich c
a
Posgrado en Oceanografía Costera, Facultad de Ciencias Marinas, Universidad Autónoma de Baja California (UABC), Apdo. Postal 76, Ensenada, B.C. 22800,
México
b
Instituto de Investigaciones Oceanológicas, UABC, Apdo. Postal 453, Ensenada, B.C. 22800, México
c
Facultad de Ciencias Marinas, Universidad Autónoma de Baja California (UABC), Apdo. Postal 76, Ensenada, B.C. 22800, México

art ic l e i nf o a b s t r a c t

Article history: Handheld X-ray fluorescence spectrometers (XRFs) represent a more practical, efficient and economic
Received 23 July 2016 tool to determine the elemental composition of solid inorganic and organic samples than conventional
Received in revised form analytical techniques. The objective of this work was to demonstrate that handheld XRFs could be a
24 August 2016
precise, accurate and reliable tool to analyze up to 27 different elements. This objective was accom-
Accepted 24 August 2016
Available online 26 August 2016
plished through the optimization of an empirical calibration curve that, in addition to include certified
reference materials (CRM), it also introduced new approaches, such as the use of solid CRM mixtures and
Keywords: combinations of organic and inorganic matrices. These approaches significantly increased the number of
Handheld X-ray fluorescence calibration points and eliminated hiatuses in the calibration curve. Several factors were evaluated before
Trace elements
construction of the calibration curve: incidence time of the X-ray beam, type of film through which the
Sediments
X-ray beams reach the samples, container type, minimum sample volume and sample moisture content.
Calibration
Organic matrices Results show that single elements can be analyzed with variable exposure times or, alternatively, mul-
tielemental analyses can be carried out with a constant exposure time (180 s). Costs can be reduced by
s
using Ziploc bags as sample containers, but the number of measurable elements drops from 27 to 21,
while the possibility of contamination increases.
& 2016 Published by Elsevier B.V.

1. Introduction
The determination of total metal concentrations in organic and
inorganic samples can be accomplished using a wide variety of
analytical techniques, such as atomic absorption spectrometry
(AAS), inductively coupled plasma-optical emission spectrometry
(ICP-OES), and X-ray fluorescence (XRF), among others with si-
milar detection limits. Except for XRF, these techniques generally
represent high investment costs (e.g., ICP-MS), significant analy-
tical effort (e.g., chemical extractions), high operational costs (e.g.,
reagents, laboratory materials, gases) and lengthy analyses times.
As for XRF, the technique has the following advantages: (1) ele-
mental concentrations can be obtained directly from the surface of
the sample; (2) requires very little preparation and analytical ef-
fort; (3) measurements are fast (seconds to minutes); (4) up to 34
different elements can be measured simultaneously (assuming
n
Corresponding author.
E-mail addresses: karla.mejia@uabc.edu.mx (K.G. Mejía-Piña),
huertam@uabc.edu.mx (M.A. Huerta-Diaz),
yajimo@uabc.edu.mx (O. González-Yajimovich).
that the concentrations are detectable); and (5) the analytical
technique is non-destructible and, thus, it allows for the sample to
be preserved for other analyses. In addition, the latest commercial
handheld XRFs available, according to the manufacturer specifi-
cations, have precisions comparable to benchtop models. The ad-
vantages of a handheld XRF, in addition to those of benchtop
models, are that it allows for direct substrate measurements in the
field, without the need to collect samples or the use of special
containers for the analyses. And finally, handheld XRFs are less
expensive than benchtop models.
Handheld XRFs are increasingly being used to analyze ele-
mental compositions in a variety of materials and matrices; for
example, rocks, soils and sediments [1–7], oyster shells [8], ar-
cheological artifacts [9,10], wood [11], and in the rapid detection of
toxic elements in liquid, solid and semisolid products regulated by
the Food and Drug Administration (e.g. food, drugs, medical in-
strumentation; [12,13]). This type of measurements have also been
effectively used in paleoenvironmental [14–16], environmental
[1,17,18] and geochemical research [19].
Although the performance of handheld XRFs has been eval-
uated previously [e.g., 18–21], these investigations have limitations

http://dx.doi.org/10.1016/j.talanta.2016.08.066
0039-9140/& 2016 Published by Elsevier B.V.
360 K.G. Mejía-Piña et al. / Talanta 161 (2016) 359–367
in their efficient application which constrain their reliable use for
optimal elemental analysis of different types of materials. Among
the most frequent limitations are: (1) calibration of a small num-
ber of elements of interest, reducing the possibility of reliable
multi-element analyses; (2) measurements based solely on the
instrument's internal calibration; (3) a priori measuring-time de-
termination based on the relative deviation as a determinant
factor; and (4) absence of criteria to establish the minimum
amount of sample that can be measured and its container material.
The objective of this work was to demonstrate that handheld
XRF instruments can be precise and reliable in the quantitative
analyses of different chemical elements. Optimal empirical cali-
brations of the equipment were obtained by careful evaluation of
the different factors involved in the determination of trace ele-
ment concentrations in marine sediments, soils, and organic ma-
trices. Several novel approaches were introduced in the calibration
process: use of solid CRM mixtures, combination of CRMs and
organic matrix samples, careful evaluation of the type of plastic
film through which the X-ray beams reach the samples, and geo-
metry of the sample container. Additionally, factors such as ex-
posure time of the X-ray beam on the sample, the sample's
minimum volume and moisture percentage were taken also into
consideration.
It is important to emphasize that the calibration developed in
this work can be applied to any kind of handheld-XRF equipment
and, possibly, to bench-top models. Before analyzing samples, it is
important to make a proper and rigorous calibration, regardless if
the equipment is used for field or laboratory work. In this way,
reproducible and high quality data will be obtained.
2. Methods
2.1. Instrument description
Analysis by XRF involves the use of an X-ray source that ir-
radiates the sample which, in turn, fluoresces due to atomic ex-
citation of the material. The incident beam must have enough
energy for the photons to collide with the inner electrons and emit
fluorescence at a specific wavelength for each element. The
Olympus Delta Premium-XRF Handheld analyzer is a 1.5 kg unit
that integrates a high resolution silicon drift detector (SDD), a 4 W
miniature X-ray tube with a rhodium anode and maximum source
current of 200 mA. The X-ray beam window has an area of
2 cm2
(1.5  1.3 cm) and a digital pulse processor. Previous to the ana-
lyses, the instrument undergoes an internal calibration process
using a piece of stainless steel 316 (Table S1). Only if the ver-
ification is passed, the instrument allows measurements to pro-
ceed. The SDD measures as counts the intensities, which are then
transformed to elemental concentrations (ppm or %) by the
software.
The instrument uses two X-ray beams to avoid spectral-peak
superpositions of the sample elements; the first beam measures
the elements V, Cr, Fe, Co, Ni, Cu, Zn, W, Hg, As, Se, Pb, Bi, Rb, U, Sr,
Y, Zr, Th, Mo, Ag, Cd, Sn and Sb, while the second measures Mg, Al,
Si, P, S, Cl, K, Ca, Ti and Mn. Depending on the sample character-
istics, the duration of the excitation time of each beam can be
modified by the user before the measurement.
2.2. Cleaning of the material
Plasticware was always used in the preparation and analyses of
each of the reference materials, which were washed with 2%
s
Micro soap and rinsed twice with deionized water. The plastic-
ware was then maintained in a 10% HCl solution for at least 72 h.
Finally the material was rinsed twice again with deionized water
and dried in a convection oven at 50 °C. A clean container was
used every time when a new sample was analyzed.
2.3. Preparation of the standards
All analyses were performed using dry samples and, when
necessary, they were grinded into a powder with the help of an
agate mortar and pestle. They were then packed in a Chemplex
s
s
1900 series plastic container, with a circular Mylar polyester film,
6.3 cm in diameter and 3.6 mm (0.14 mil) thickness. The lower or-
ifice of the container was covered with the polyester film and,
with the help of two rings of the same material, a taut wrinkle-free
sample support window was created. The container was then fil-
led with the sample material though the upper orifice, gently
pressing it to obtain a compact sample. Lastly, the upper orifice
s
was covered with the same type of Mylar polyester film and
closed with a lid of the same material as the container.
2.4. Reference materials
A total of 33 samples were used for the XRF calibration pro-
cedure (Table 1) and these included certified reference materials
(CRM) with inorganic (SS-CRM) and organic (O-CRM) matrices. A
series of in-house standards representing samples from different
environments were also analyzed; these included sediment sam-
ples (SS-RM) and organic matrices (microbial mats; O-RM), whose
trace metal concentrations were measured by atomic absorption.
Finally, as a novel contribution of this work, we included among
the 33 analyzed samples a series of CRM mixtures (M-CRM) that
were prepared by mixing the CRMs Metals in Soil (CRM1) and
PACS-2 (CRM2) in the mass proportions (CRM1:CRM2) 1:1, 1:3, 3:1
and 1:7. The in-house standards corresponded to samples with
previously reported concentrations [22–25], or samples analyzed
in our Sediment Biogeochemistry Laboratory (samples AGC-E7,
BTS-21 y BTS-7). All the in-house standards were digested by the
total chemical extraction procedure described by [26], and their
concentrations obtained by flame atomic absorption spectrometry
(Varian model AA240FS); Mo and V concentrations were de-
termined with graphite furnace atomic absorption spectrometry
(Varian model AA880Z) because the internal reference material
concentrations were below the detection limits of the flame
atomic absorption spectrometer. Finally, total (Ct) and inorganic
carbon (Ci) concentrations were measured in both organic CRMs
and organic samples (Table 1), using a CO2 coulometer (UIC, Inc.
Model CM150) equipped with acidification and combustion
modules. Organic carbon (Corg) was calculated as the difference
between Ct and Ci. Calibration of the equipment with a CaCO3
s
powder standard (Mallinckrodt 4072) produced a percent re-
covery of 101.63 70.62% (n ¼6). Blanks were always below the
detection limit of the instrument (8.8  10  3 mg C).
2.5. Incidence time of beams 1 and 2
Since the handheld XRF uses two excitation X-ray beams whose
duration can be modified based on the analytical requirements,
exposure time tests were performed by measuring in quintuplicate
(except for the 180 s time that was measured in triplicate) the
standards at different time intervals (5, 10, 20, 30, 60 and 180 s).
These tests were performed based on the assumption that longer
times would achieve better resolution of the spectral peaks, which
in turn could result in decreasing detection limits of the elements
of interest. Based on the average results, calibration curves were
constructed for each element and for each time considered, so that
optimal measuring times could be determined.
 K.G. Mejía-Piña et al. / Talanta 161 (2016) 359–367 361

Table 1
Inorganic certified reference materials (CRM), CRM mixtures, organic CRMs, and in-house standards (sediment and organic samples) used in the handheld XRF instrument
calibration used in this work. Organic carbon values, which were measured in this work, are included for reference purposes.

No. Code Description

Sediment and soil CRMs (SS-CRM)

1 PACS-2 Marine sediment CRM for trace metals and other constituents collected in Esquimalt Harbor, British Columbia, National Research Council of Canada
(NRCC).
2 MESS-3 Marine sediment CRM for trace metals and other constituents from Beaufort Sea, NRCC.
3 HISS-1 Marine sediment CRM for trace metals and other constituents from Hibernia Shelf, NRCC.
4 BCSS-1 Marine sediment CRM for trace metals and other constituents collected in Baie des Chaleurs, Gulf of St. Lawrence, NRCC.
5 TM-FWS Trace metals in fresh water sediment CRM, Sigma-Aldrich.
6 ES-1646a Estuarine sediment CRM for major, minor and trace elements, National Institute of Standards and Technology (NIST).
7 NIST-2702 Inorganics in marine sediments collected at the mouth of Baltimore Harbor, NIST.
8 MS Metals in soil, Environmental Resources Associates (ERA), Lot # D079.
9 TCLP Soil Inorganic trace metals in soil (PriorityPollutnT™), Lot #239, ERA.

Sediment CRM mixtures (m-CRM)

10 Mixture 1 Mixture MS:PACS-2 (1:1 ratio).
11 Mixture 2 Mixture MS:PACS-2 (1:3 ratio).
12 Mixture 3 Mixture MS:PACS-2 (3:1 ratio).
13 Mixture 4 Mixture MS:PACS-2 (1:7 ratio).

Sediment samples (SS-RM)

14 MTX-2 Deep marine sediments, northwestern coast of Baja California Peninsula, Mexico,[22].
15 MTX-3 Deep marine sediments, northwestern coast of Baja California Peninsula, Mexico,[22].
16 RP-43 Marine sediments, port of Ensenada, Baja California, Mexico, [23].

Sediment samples (SS-RM) (cont.)

17 RP-104 Marine sediments, Port of Ensenada, Baja California, Mexico, [23].
18 SAUZAL Marine sediment, Port of El Sauzal, Baja California, Mexico, [23].
19 XIXIMI-1 Deep marine sediment, Gulf of Mexico, [24].
20 XIXIMI-2 Deep marine sediment, Gulf of Mexico, [24].
21 XIXIMI-3 Deep marine sediment, Gulf of Mexico, [24].
22 AGC-E6 Marine sediment, Upper Gulf of California, unpublished data.
23 AGC-E7 Marine sediment, Upper Gulf of California, unpublished data.
24 BTS-21 Marine sediment, Todos Santos Bay, Mexico, unpublished data.
25 BTS-7 Marine sediment , Todos Santos Bay, Mexico, unpublished data.

Organic CRMs (O-CRM)

26 Sargasso Biological CRM of Sargassum fulvellum, Shimoda Bay, Japan; National Institute for Environmental Studies (NIST; Corg: 27 mmol g  1).
27 Tomato CRM of tomato leaves for major, minor and trace elements in botanical materials (NIST; Corg: 29 mmol g  1).
28 Citrus-1572 CRM of citrus leaves for major, minor and trace elements in botanical materials (NIST; Corg: 33 mmol g  1).
29 Tissue-2976 CRM of mussel tissue for trace elements and methylmercury in marine bivalve mollusk tissue (NIST; Corg: 29 mmol g  1).

Organic samples (O-RM)

30 Lyngbya 3 Hypersaline Lyngbya sp. microbial mat, tidal creeks of Ojo de Liebre Lagoon, Baja California Sur, Mexico (Corg: 4.5 mmol g  1), [25].
31 LF01 3 Hypersaline microbial mat, Figueroa Lagoon, Baja California, Mexico (Corg: 5.5 mmol g  1), [25].
32 P5 B2 Hypersaline microbial mat, tidal creeks of Ojo de Liebre Lagoon, Baja California Sur, Mexico (Corg: 4.2 mmol g  1), [25].
33 LF01 2 Hypersaline microbial mat, Baja California, Mexico, (Corg: 6.5 mmol g  1), [25].

2.6. Calibration curves 2.7. Selection of the layer thickness to be analyzed

Linear regression analyses calculated using the Pearson model The best sample thickness of the material to be analyzed was
included both curves passing through the origin and those with an investigated since this factor is a function of the material's density
s

intercept in the independent variable axis. The values obtained by and container geometry. Five Chemplex plastic containers with
s

the equipment (dependent variables) were compared to the re-
ported reference values (independent variables), all of these in
mmol g  1 concentration units. We report also statistical para-
meters such as Pearson correlation coefficient, number of ob-
servations (n), significance of the Pearson correlation (P), slope of
the curve (m), intercept with the ordinate axis (a), standard error
(SE) of m and a, and relative standard error of the slope
(SRE ¼SE*100/m). For each analyzed element, the operational lin-
ear working range and its detection limit (DLcal) were obtained.
The parameter DLcal was defined as three times the standard de-
viation of the average of all the measurements that were used in
Mylar plastic film were used in the thickness selection. Each
container was filled with 0.5, 1.0, 1.5, 2.0 or 3.0 g of the certified
reference material MESS-3, corresponding to thicknesses of 0.2,
0.4, 0.6, 0.8 and 1.2 cm, and equivalent to volumes of 2.0, 4.0, 5.9,
7.9 and 12 cm3. Each sample was analyzed with a constant 180 s
exposure time.
2.8. Type of plastic film through which X-ray beams reach the
sample and geometry of the container
Three types of plastic films of different composition and
thickness were used to evaluate their effect in the analyses results:
s

the construction of a given calibration curve [20]. Also, it was (1) Mylar polyester film, 6.3 cm in diameter and with a constant
available the detection limit provided by the equipment's manu- thickness of 3.6 mm; (2) two food grade commercial plastics,
s s s

facturer (DLXRF). Pétalo and Store it brands; and (3) Ziploc type 1″  1″
(2.5  2.5 cm) plastic bags. Trials (1) and (2) involved the use of
s
three Chemplex containers covered with each of the plastic films
362 K.G. Mejía-Piña et al. / Talanta 161 (2016) 359–367

s s s
mentioned above (Mylar , Store it and Pétalo ). All trials were
carried out using an exposure time of 180 s and involved con-
tainers with and without sample. The CRM MESS-3 was the only
s
sample analyzed in the three trials, with
2.0 g for the Chemplex
s
container with Mylar and commercial plastic, and
1.0 g for the
s
Ziploc type bags. The last amount of sample is the minimum
necessary to make measurements with this type of bag. Ad-
ditionally, the possibility of a more practical and economical way
to operate the XRF was investigated by comparing two types of
s
containers with different acquisition costs: (1) Chemplex con-
s s
tainers covered with Mylar film, and (2) Ziploc type 1″  1″
(2.5  2.5 cm) plastic bags that can be locally purchased. Both
containers were already described.
2.9. Moisture test
Another factor that can potentially influence the XRF analysis
precision is the sample moisture content. To evaluate this factor,
the results of the analyses of MESS-3, PACS-2 and HISS-1 before
and after they were kept in a convection oven at 65 °C during 24 h,
were compared.
3. Results and discussions
We were unable to construct calibration curves for six (Y, Zr, W,
U, Bi and Th) of the 34 measurable elements because at least four
CRMs with detectable concentrations of a given element are
needed to build a reliable calibration curve. For the special case of
Mg, although there were reported values of this element for 12
CRMs (31–605 mmol g  1), no readings were obtained with the
instrument, most likely because their concentrations were below
the instrument's detection limit (DLXRF) which, unfortunately, is
not reported by the manufacturer. The other 27 elements (V, Cr, Fe,
Co, Ni, Cu, Zn, Hg, As, Se, Pb, Rb, Sr, Mo, Ag, Cd, Sn, Sb, Al, Si, P, S, Cl,
K, Ca, Ti, Mn) were detected by our handheld XRF.
Results obtained from calibration curves adjusted to the origin
and with those including the Y-intercept value, allowed to select
the best fitted curves to quantify the various elements (e.g., Fig. 1).
The criteria used to select the best calibration curves were the
following statistical parameters, arranged in their order of im-
portance: number of observations (n), correlation coefficient (R),
statistical significance (P), intercept with the ordinate axis (a) and
relative standard error of the slope. The number of standards used

Fig. 1. Examples of calibration curves obtained with the handheld XRF instrument (continuous lines), which include Pearson correlation coefficients (R) and number of
observations (n) for: (a) Zn without Y-intercept; (b) Zn with Y-intercept; (c) Fe without Y-intercept; and (d) Fe with Y-intercept. Samples used in the calibrations included:
sediment and soil certified reference materials (SS-CRMs), sediment and soil samples (SS-RM), sediment CRM mixtures (M-CRM), organic CRMs (O-CRM) and organic
samples (O-RM). For a full description of the different samples, see Table 1. Insert shows Fig. 1a, but with an expanded scale.
 K.G. Mejía-Piña et al. / Talanta 161 (2016) 359–367 363

in the linear regression analysis was considered to be the most
important parameter, since the larger this number is, the most
reliable the calibration curve will be and, additionally, it de-
termines the linear working range of the measurements. The next
two parameters (R and P) determine how robust the fitness of the
regression model is: low correlation coefficient values are attrib-
uted to factors such as the lack of homogeneity of the sample and
low element concentrations compared to the instrument's detec-
tion limit. It should be noted that since R values for curves ad-
justed to the origin are not meaningful from the statistical point of
view [27], statistical programs and spreadsheets are unable to
provide this parameter. The next criterion was to select curves
adjusted to the origin over curves with an intercept on the ordi-
nate axis, under the assumption that values extrapolated to each
axis should coincide with the origin. Curves with intercepts in any
of the axis would imply the presence of negative values, either of
the instrument's counts or in the standard's concentrations. Fi-
nally, under equal conditions, the regression analysis with the
lowest RSE was chosen as the best calibration curve. The statistical
parameters of the calibration curves (adjusted to the origin, or not)
for all the analyzed elements at different times of exposure, are
available as supplementary information (Table S2).
The results obtained with the various parameters were sepa-
rated in two groups: the first group includes the best results that
were obtained based on the above mentioned criteria with and
without intercept to the ordinary axis (Tables 2a and 2b, respec-
tively), which can be used for measuring a limited number of se-
lected elements, thus obtaining optimal results of their con-
centrations. All measured elements show their best parameters
when they are fitted to the linear regression model that intercepts
the origin (Table 2b), except for P and Si which have their best
statistical parameters (R and P) when their curves intercept the
ordinate axis (Tables 2a); the RSE decreases 3% for P when its curve
is not adjusted to the intercept, whereas for Si the error percen-
tage is 9.7% higher when there is no fit to the origin. A total of 54
(27 pairs) significant linear regressions were obtained for all the
27 detected elements. As shown in Tables 2a, the range of R values
was 0.761 (Ni) to 0.997 (Se), with calibration curves that included
a minimum of four (Rb) and a maximum of 29 (Fe) observations
(n). The statistical significance (P) of the correlations was always
very robust, since for the 54 linear regressions shown in Tables 2a
and 2b, 47 (87%) had values of P r0.001, five (9%) had values of
0.001o Pr0.01, and only two (4%) had values of 0.01 oP r0.05.
Finally the RSE values associated to the slope were between 3.2%
and 38% without adjustment to the origin (Tables 2a) and between
2.2 and 19% with adjustment (Table 2b); however 41 (76%) of the
54 regressions showed RSE values o10% (Tables 2a and 2b).
The second group of results included the best parameters sui-
table for multielemental measurements (Table S3), all of them
requiring an exposure time of 180 s. This counting time selection
was based in the fact that of all the 27 elements considered in
Table 2, the predominant optimal exposure time (37% of the total,
equivalent to 10 elements) was 180 s. The rest of the exposure
times considered (5, 10, 20, 30 and 60 s) represented only 7–19% of
the total (Table 2). Of the 54 obtained linear regressions, only two
(Cl, with and without intercept to the ordinate axis) were not
statistically significant (P 40.05). The R range for the other 52
curve fits (Table S3) was 0.761 (Ni) to 0.997 (Se), with statistical
significances of P r0.001 for 42 (81%) of the calibrations; eight
(15%) with 0.001 oPr 0.01, and only two (4%; Ni, Rb) with
0.01 oP r0.05. Of the 52 curve fits shown in Table S3, 71% (37)
showed RSE values o10%, with a range of values of 2.3% (Mn, Se)
to 38% (Ni), while the range for the DLcal was between 0.0039 (Hg)
and 15 (Si) mmolg  1 (Table S3). Interestingly, the results shown in
Tables2 and S3 demonstrate that longer exposure times not ne-
cessarily result in better estimations of elemental concentrations

Table 2a
Optimal statistical parameters and exposure times (T) for each of the analyzed elements. Included are linear regressions without adjustment to the origin.

Element n R a P m7 SE RSE (%) OLWR (lmol g  1) DLcal (lmol g  1) DLXRF (lmol g  1) T (s)

Ag 6 0.993 0.022 70.023 * 1.064 70.063 5.9 0.12–0.618 0.013 0.56 180
Al 16 0.944 (0.11 71.5)x102 * 0.6827 0.064 9.3 (1.5–26.6)x102 39 na 20
As 13 0.990 0.080 70.055 * 1.1957 0.051 4.3 0.069–3.10 0.019 0.093 60
Ca 16 0.971 977 88 * 1.097 7 0.072 6.5 (0.35–33.2)x102 7.5 na 10
Cd 6 0.993 0.022 70.029 * 0.825 7 0.049 6.0 0.080–1.03 0.022 0.36 180
Cl 6 0.976 9.3 73.8 * 3.60 7 0.40 11 (2.8–62.3)x102 12 71 60
Co 9 0.925 0.87 70.87 * 10.8 71.7 16 2.5–6.90 0.35 1.1 30
Cr 13 0.975 0.117 0.12 * 0.7427 0.051 6.8 0.66–5.21 0.12 0.49 180
Cu 26 0.985 0.167 0.077 * 1.1677 0.042 3.6 0.14–5.37 0.075 0.68 20
Fe 29 0.977 567 27 * 1.1307 0.047 4.2 (0.022–16.2)x102 4.2 1.8 10
Hg 12 0.944 0.0042 70.0016 * 6.75 7 0.75 11 0.011–0.367 0.0039 0.055 180
K 13 0.961 7.3 7 6.3 * 1.25 7 0.11 8.7 (0.21–19.4)x102 2.1 na 60
Mn 22 0.990 0.767 0.47 * 1.0117 0.032 3.2 0.99–399.0 0.33 0.51 30
Mo 16 0.982 0.023 70.0081 * 0.934 7 0.048 5.2 0.018–0.439 0.0043 0.073 180
Ni 7 0.761 0.99 70.86 1.46 7 0.56 38 0.32–2.79 0.045 0.75 180
P 9 0.917 897 9.4 * 0.5707 0.094 16 91–253 5.2 (8.1)x102 10
Pb 22 0.975 0.018 70.025 * 1.089 7 0.055 5.1 0.019–0.911 0.0073 0.063 60
Rb 4 0.984 0.137 0.12 1.077 0.14 13 0.067–1.44 0.021 0.07 10
S 9 0.917 77 736 * 0.63 7 0.10 16 (0.44–4.57)x10  2 5.5 (4.1)x102 5
**
Sb 6 0.961 0.177 0.15 2.137 0.31 14 0.13–1.94 0.036 0.78 180
Se 8 0.997 0.00187 0.0202 * 1.1627 0.038 3.3 0.016–1.30 0.0048 0.1 180
Si 5 0.973 (3.27 1.6)x103 ** 0.99 7 0.14 14 (60–124)x102 40 na 20
Sn 7 0.953 0.093 70.109 * 1.047 0.15 14 0.15–1.51 0.029 0.67 180
Sr 10 0.966 0.085 70.183 * 0.981 7 0.092 9.4 0.92–2.88 0.017 0.057 30
Ti 9 0.976 14.4 7 6.2 * 0.758 7 0.064 8.5 17–156 1.8 3.1 30
V 10 0.817 2.107 0.72 ** 0.86 7 0.22 25 2.6–8.15 0.27 na 180
Zn 26 0.966 0.127 0.16 * 0.989 7 0.054 5.5 0.071–7.09 0.063 0.31 20
Minimum 4 0.761 – – – 3.2 – 0.0039 0.055 5
Maximum 29 0.997 – – – 38 – 40 (8.1)x102 180

n¼ number of observations; R¼ correlation coeficient; P ¼statistical significance.

**
0.001 oP r 0.01.
*
Pr 0.001.
364 K.G. Mejía-Piña et al. / Talanta 161 (2016) 359–367

Table 2b
Optimal statistical parameters and exposure times (T) for each of the analyzed elements. Included are linear regressions with adjustment to the origin (a¼ 0).

Element n R P m7 SE RSE(%) OLWR(lmol g  1) DLcal (lmol g  1) DLXRF(lmol g  1) T (s)

*
Ag 6 nc 1.1177 0.029 2.6 0.12–0.618 0.013 0.56 180
*
Al 16 nc 0.7257 0.026 3.6 (1.5–26.6)x102 39 na 20
*
As 13 nc 1.1417 0.036 3.2 0.069–3.10 0.019 0.093 60
*
Ca 16 nc 1.149 7 0.054 4.7 (0.35–33.2)x102 7.5 na 10
*
Cd 6 nc 0.853 7 0.031 3.6 0.080–1.03 0.022 0.36 180
*
Cl 6 nc 3.617 0.23 6.3 (2.8–62.3)x102 12 71 60
*
Co 9 nc 9.167 0.39 4.2 2.5–6.91 0.25 1.1 60
*
Cr 13 nc 0.776 70.029 3.7 0.66–5.21 0.12 0.49 180
*
Cu 26 nc 0.8017 0.022 2.8 0.14–5.37 0.075 0.68 20
*
Fe 29 nc 1.2067 0.032 2.6 (0.022–16.2)x102 4.2 1.8 10
*
Hg 12 nc 6.62 70.52 7.8 0.011–0.367 0.0039 0.055 180
*
K 13 nc 1.239 7 0.067 5.4 (0.21–19.4)x102 2.1 na 60
*
Mn 22 nc 1.048 7 0.023 2.2 0.99–39.0 0.33 0.51 30
*
Mo 16 nc 1.025 7 0.042 4.1 0.018–0.439 0.0043 0.073 180
**
Ni 7 nc 0.84 70.16 19 0.32–2.79 0.045 0.75 180
*
P 9 nc 1.177 0.22 19 43–252 2.1 (8.1)x102 60
*
Pb 22 nc 1.061 70.038 3.6 0.019–0.911 0.0073 0.063 60
**
Rb 4 nc 1.023 7 0.080 7.9 0.062–1.45 0.029 0.07 5
S 9 nc *
0.828 7 0.060 7.3 (0.44–4.57)x10  2 5.5 (4.1)x102 5
*
Sb 6 nc 1.85 7 0.17 8.9 0.13–1.94 0.036 0.78 180
*
Se 8 nc 1.164 7 0.026 2.3 0.016–1.30 0.0048 0.1 180
*
Si 5 nc 0.7237 0.031 4.3 (60–122)x102 81 na 5
*
Sn 7 nc 0.934 7 0.079 8.5 0.15–1.51 0.029 0.67 180
*
Sr 10 nc 1.020 7 0.036 3.5 0.92–2.88 0.017 0.057 30
*
Ti 9 nc 0.8917 0.036 4.0 17–156 1.8 3.1 30
*
V 10 nc 1.42 7 0.14 9.8 2.6–8.15 0.27 na 180
*
Zn 26 nc 1.0217 0.033 3.3 0.071–7.09 0.063 0.31 20
Minimum 4 – – – 2.2 – 0.0039 0.055 5
Maximum 29 – – – 19 – 81 (8.1)x102 180

n¼ number of observations; R ¼correlation coeficient; P ¼ statistical significance.

(***0.01o P r 0.05); m ¼ slope; SE ¼ standard error associated with the slope; RSE ¼ relative standard error (calculated as SE*100/m); OLWR ¼operational linear working
range; DLcal ¼ calculated detection limit; DLXRF ¼ detection limit provided by the manufacturer; na ¼not avaible and nc ¼not computable (the statistical program was unable
to calculate the value).
*
Pr 0.001.
**
0.001 oP r 0.01.

(e.g., S and Rb), contrary to Dahl et al. [15] who mentioned that
XRF analytical precision improves with longer exposure times.
Considering that the predominant time of exposure for multi-
elemental measurements was 180 s, we opted to use this time
setting for all of the other trials.
Initially, we assumed that longer exposure times would yield
better detection limits; however, as shown in Table 3, the results of
our calculated detection limits (DLcal) demonstrate that, even with
short exposure times (5 s for all cases) the detection limits pro-
vided by the manufacturer (DLXRF) were higher than those ob-
tained in this study for 12 (80%) of the 15 elements for which a
comparison could be made, and lower for three (20%) of them,
with DLcal values between 0.026 and 84 mmol g  1. For the specific
case of Al, Ca, K, Si and Zn, the DLXRF values were not provided by
the manufacturer, so the values obtained in this study could be a
good approximation of this parameter, at least for our particular
handheld XRF analyzer. The DLcal for Ag, Cd, Co, Cr, Ni, Sb, Sn and V
are not reported since their linear regressions were not statistically
significant for the 5 s exposure time (Table 3). Finally, comparison
of the DLcal obtained with the optimal results shown in Table 2,
shows that our value is lower than the DLXRF provided by the
manufacturer for all elements, except Fe that has a DLcal that is
2.4 mmol g  1 larger than the manufacturer's DLXRF.
An element by element goodness of fit test was applied to the
results obtained in the trial involving selection of the thickness of
the sample layer to be analyzed, based on a homogeneity model
that integrates the differences between observed and expected
values [null hypothesis (H0): observed values ¼expected values;
alternate hypothesis (Ha): observed values≠expected values]. This
test compares if both observations are equal or different to each
other through the following mathematical expression:
k
(observed − expected)2
2
Xcal = ∑ ,
1
expected (1)
2 2
Xcri = X 0.95, k −1 (2)
where k refers to the total of categories of classes to be compared.
To accomplish our objective, two different tests with different
hypothesis were proposed. The first establishes that the observed
values (corresponding to the results obtained by analyzing 1.0, 1.5,
2.0, and 3.0 g of CRM MESS-3; k ¼4) are equal (P ¼95%) to the
result obtained analyzing only 0.5 g of the same CRM. The second
test establishes that the results obtained measuring 1.0, 1.5,
2.0 and 3.0 g (k ¼5) are all equal.
Results obtained from the first test (Table S4), where H0:
0.5 ¼1.0¼1.5¼2.0 ¼ 3.0 g, demonstrate that 46% of the times (11 of
24 elements compared) H0 is rejected, thus indicating that there
are significant differences (P ¼95%) between the two groups of
elements. The second hypothesis (H0: 1.0 ¼1.5¼2.0 ¼ 3.0 g), how-
ever, is accepted by 100% of the observations, implying that there
are no statistically significant differences (P ¼95%) among the va-
lues obtained for each of the elements, regardless of the layer
thickness of the sample, provided this layer is 40.4 cm thick
(equivalent to 1.0 g, or 2.0 cm3 for the CRM MESS-3). These results
agree with those reported by Kalnicky and Singhvi [20], who
found that the maximum depth of X-ray penetration is
2 mm for
a soil matrix, since they assumed that a 45 mm layer thickness
can be considered as infinitely thick for this type of analysis.
The test results using plastic films of different composition and
thickness in empty containers indicated that the most suitable
 K.G. Mejía-Piña et al. / Talanta 161 (2016) 359–367 365

Table 3
Difference between calculated detection limits (DLcal) and those provided by the
manufacturer (DLXRF) for an exposure time (T) of 5 s.
1.9–38% range (Cu and S, respectively). The DLcal range was from
0.012 (Hg, Pb) to 19 (Cl) mmol g  1. It is worth noting that although
the elements Al, Co, Ni, Sr and V showed instrumental detectable
s

Element P T(s) DLcal DLXRF DLXRF  DLCal (lmol values, the calibration curves obtained with Ziploc type bags are
(lmol g  1) (lmol g  1) g  1) disperse and, as a consequence, are not statistically significant
(P 40.05). Although our results show that it is feasible to analyze
Ag ns 5 0.036 0.56 0.52 21 elements with these bags as sample containers, it is important
*
Al 5 84 na – s

As *
5 0.071 0.093 0.022
to consider that the composition of the empty Ziploc bags can
Ca *
5 11 na – vary and that they contain contaminant elements (e.g., Al, Si, Cl, K,
Cd ns 5 – 0.356 – Ca, Sr, Y, Zr, Ag and Cd; Table S5) that represent a source of error in
**
Cl 5 42 71 29 the determination of total metal concentrations of a sample.
Co ns 5 – 1.1 –
Although the calibration curves obtained with the use of
Cr ns 5 – 0.49 – s s

Cu *
5 0.16 0.68 0.52 Mylar plastic film and Ziploc type bags are equivalent for some
Fe *
5 5.9 1.8  4.1 elements (e.g., compare Tables S3 and S6), it is important to con-
**
Hg 5 0.028 0.055 0.027 sider that bags can only be used for determining those elements
*
K 5 7.1 na – which are detectable with these types of bags, and only if both
*
Mn 5 0.82 0.51  0.31
Mo *
5 0.028 0.073 0.045
calibration standards and sample materials are analyzed using the
Ni ns 5 – 0.75 – same type of container. This strategy implies that the costs of
P **
5 7.6 807 799 analyses could be considerably decreased for those elements de-
* s
Pb 5 0.026 0.063 0.037 tectable with Ziploc type bags, since they are more economical
***
Rb 5 0.029 0.07 0.041 s s

* and easier to acquire than Chemplex containers with Mylar film.

S 5 5.5 405 400
Sb ns 5 – 0.78 – However, care should be taken when using plastic bags since the
Se *
5 0.032 0.1 0.068 possibility of important contributions from contaminant elements
** s
Si 5 81 na – will exist, depending on the brand of Ziploc bag used.
Sn ns 5 – 0.67 – Four additional tests of goodness of fit were carried out that
*
Sr 5 0.041 0.057 0.016
Ti *
5 4.4 3.1  1.3
compared if the element by element results obtained were (1) all
Zn *
5 0.13 na – equal among themselves, regardless of the type of film used in the
s s s s
V ns 5 – 0.31 – analyses (H0: Mylar ¼Store it ¼ Pétalo ¼Ziploc ; type: k ¼4;
s
P¼ 0.95); or (2) if the results obtained with Mylar film were
P¼ statistical significance.
*
equivalent (k¼ 2; P¼ 0.95) to those obtained with each of the other
Pr 0.001. s s

** three plastics tested: (a) H0: Mylar ¼Pétalo , (b) H0:

0.001 oP r 0.01.
***
0.01 oP r 0.05; ns ¼ not significant); na ¼not available.
s
plastic is Mylar . Our results demonstrate that plastic films such as
s s s
Pétalo , Store it , and Ziploc type bags contain more “impurities”
s s
than the Mylar plastic film (Table S5). Of the 34 elements ana-
lyzed with the instrument, 20 (Ag, Al, As, Ca, Cd, Cl, Cu, K, Mo, Ni, P,
Rb, S, Si, Sr, Th, U, Y, Zn, Zr) were detected as impurities, with at
least 18 (90%) being part of the elemental composition of the
s s
kitchen plastics (Pétalo and Store it ) and 10 (50%) of the Ziploc
type bags, compared to only six (30%) detected in the Mylar
plastic film, four of which (Ni, P, Si, Zn) presented values under the
DLcal. In addition to the error introduced by the composition of the
s
commercial plastics, an added advantage of the Mylar film is the
homogeneity of its thickness (3.6 mm), which guarantee geometry
consistency between measurements.
To test if there was a more practical and economical way to
measure elemental concentrations with the handheld XRF, cali-
bration curves were constructed using both Chemplex containers
s s
with Mylar film (Table S3) and Ziploc type plastic bags (Table
S6). Due to the high number of interfering elements present as
impurities, no calibration curves were constructed using Pétalo
s
and Store it plastic films (Table S5). Generally speaking, there was
a reduction in the number of elements that can be calibrated when
s s
using Ziploc type bags as compared to those with Mylar plastic
film (Table S6). With this film, statistically significant curves were
constructed for a total of 26 elements (exposure time: 180 s),
s
while curves for only 21 elements were possible for Ziploc type
bags, using the same exposure time of 180 s. The range of R values
for this case was between 0.730 (S) and 0.997 (Se), with calibration
curves that included a minimum of four (Rb) and a maximum of
28 (Fe) observations (n). The statistical significance of the corre-
s
lation (P) for the Ziploc type bags was r0.001 for 38 (90%) of the
constructed curves, two (5%; Cl and Rb) with 0.001 oP r0.01, and
two (5%; P and Rb) with 0.01 oP r0.05, with RSE values in the
s s s s
Mylar ¼Store it , and (c) H0: Mylar ¼ Ziploc type. Results from
test (1) indicate that the values obtained for each of the plastics
were all different to each other (i.e., H0 was rejected 100% of the
times), implying that there are statistically significant differences
(P ¼95%) among the four different materials used. Test (2a) in-
dicates that measurements made with Pétalo brand plastic are
s
statistically different to those obtained with Mylar film for all
(100%) the elements tested. Test (2b) indicates that measurements
s s
made with Mylar film and Store it brand plastics are the same
s
for 91% of the elements. Lastly, test (2c) indicates that using
s s s
Ziploc type bags is equivalent to using Mylar film for 68% of the
analyzed elements (Table S7).
As mentioned before, moisture can influence the precision of
the analyses, so a comparison of the results (element by element)
of the CRMs MESS-3, PACS-2 and HISS-1 before and after drying
was carried out. Drying was accomplished by subjecting all sam-
ples to a temperature of 65 °C during 24 h in a convection oven.
Comparison of results was done using a goodness of fit test based
on a homogeneity model (H0: before¼ after). Our results showed
no significant differences between the samples before and after
the drying period, since H0 was accepted 100% of the times for the
s
CRMs MESS-3 and HISS-1% and 96% of the times for PACS-2. Fur-
thermore, the measured moisture percentages were very small,
representing only 1.7%, 0.35% and 0.36% for PACS-2, MESS-3 and
HISS-1, respectively. These results can have important implications
during field measurements (e.g., soils), since moisture contents
can easily could be higher than the 0.35–1.7% obtained in our la-
boratory tests. More moisture content in the samples implies more
dilution of the solid samples, with its consequent decrease in the
real concentration of the elements; this error could be insignif-
icant in samples with little moisture content (e.g., 5–20%; [20]),
but the error could be important for samples with moisture
content 420%, which should be dried [20]. Samples that have
been adequately dried and stored for long periods of time (years)
do not have to be necessarily oven-dried again before measuring
366 K.G. Mejía-Piña et al. / Talanta 161 (2016) 359–367

them by XRF; however, it is recommended that an evaluation of
moisture content be made before the analysis. If results show
important water contents (e.g., 45%), then it is recommended to
dry the samples under the previously mentioned conditions. Fi-
nally, the results of our moisture tests suggest that if the hand-
held-XRF instrument is used on location (field measurements), it is
advisable to subsequently compensate for the effects of humidity
content [e.g., 28].
It is common practice that in constructing calibration curves
with an XRF instrument it is required to use organic CRMs to
analyze samples with organic matrices, while for samples with
inorganic matrices it is required to use only inorganic CRMs.
Possible organic matrix effects could be the result of variations in
the concentrations that the interfering elements have on the X-ray
intensity emitted by the elements of interest [20]. Nevertheless,
our results suggest that both matrix types can be combined, ap-
parently without affecting the calibration curve for several se-
lected elements, as shown in the examples of Fig. 1. The criteria
that were applied to decide if organic standards could be used in
the construction of a given calibration curve were that: (1) at least
one of these standards was found within the operational linear
working range (OLWR) of the instrument; (2) its concentration
should be between at least two inorganic standards; and (3) the
number of observations that make up the calibration curve should
be increased without substantially affecting the correlation coef-
ficient (R) and statistical significance (P) previously calculated
without the inclusion of the organic standards.
Our results suggest that, without distinction, organic (Sargasso,
Tomato, Citrus-1572, Tissue-2976, microbial mats) and inorganic
matrices (Table 1) can be used for the construction of calibration
curves. These results will be discussed only for 14 of the 27 ele-
ments calibrated, since only they met the three criteria mentioned
above for the construction of these calibration curves. Our results
showed that inclusion of organic standards increased the number
of observations in the curves for the 14 considered elements (Al,
As, Ca, Cl, Cu, Fe, K, Mn, Mo, P, Pb, Rb, S, Zn). These increments
represented from one to eight additional observations per element
(difference between the n values shown in Table 4). The range of
the correlation coefficients (R) for linear regressions, adjusted to
the origin and using organic and inorganic matrices, varied from
Table 4
Statistical parameters R, n and P for calibration curves constructed with (OIM) and
s s
without (IM) organic standards, using Chemplex containers with Mylar film and
the best exposure times (T) obtained from Table 2. All calibration curves pass
through the origin, except phosphorus, for which its Y-intercept is 120 7 33.
0.917 (P) to 0.990 (As, Mn). Our results also indicate that correla-
tion coefficients decreased only for two elements (Mo, S), but the
difference between both coefficients was not substantial in any of
the cases (differences between R′s o0.045). For the special case of
Cl and Rb, construction of calibration curves would not have been
possible without combining both matrices, since there were only
two inorganic standards available for both elements. For the ele-
ments Al, As, Ca, Cu, Fe, K, Mn, Mo, P, Pb, Rb, and Zn, the value of R
increased or remained the same with the addition of organic
matrix standards (Table 4, Fig. 1).
Finally, one of the main challenges when making methodolo-
gical calibrations of a XRF instrument is the limitation in the
number of available certified standards. In this work, as mentioned
before, four solid mixtures of CRMs (M-CRM) were prepared by
combining the standards Metals in soil (CRM1) with PACS-2
(CRM2) in the proportions (CRM1:CRM2) 1:1, 1:3, 3:1 and 1:7. This
new approach can be advantageously used to increase the number
of available certified standards and/or to eliminate hiatus present
in the calibration curve of a particular element. The mixtures
prepared in the way previously described represent 21 (78%) of the
27 calibration curves obtained using Chemplexs plastic containers
and Mylars plastic films. Hence, of the 22 elements that were
present in both standards and for which their concentrations were
calculated in the mixtures, 21 (Ag, Al, As, Ca, Cd, Co, Cr, Cu, Fe, Hg,
K, Mn, Mo, Ni, Sb, Se, Sn, Sr, Ti, V, Zn) had at least one value
contributed to their calibration curves by one the CRM mixtures.
These results demonstrate that the use of solid mixtures is an ef-
fective, viable, economical and practical method for the con-
struction of more robust calibration curves when using a handheld
(or benchtop) XRF instrument.
4. Conclusions
Handheld XRF instruments are a dependable tool to determine
the elemental composition of solid samples. Our results show that
the developed methodology can be applied to different types of
solid sample matrices with reliable results based on the user's
needs. The optimal analytical conditions recommended to be ap-
plied to all analyses (standards and samples) are the following:
thickness of the sample layer 40.4 cm, use of special containers
for XRF measurements (e.g., 6.4 cm Chemplexs) with special
s
plastic film (e.g., 3.6 mm Mylar Polyester), moisture content o5%
in the sample and standards, and grain (or particle) size as uniform
as possible. It is possible to carry out analyses with other types of
s

Element T (s) OIM IM

sample containers (e.g., Ziploc type bags), provided that stan-
dards and samples are consistently analyzed with the same type of
R n P R n P bags. However, use of other types of sample containers opens the
* *
possibility of substantial contributions from contaminating ele-
Al 20 0.944 16 0.923 15
As 60 0.990 13 0.990 11 * ments (e.g., Al, Si, Cl, K, Ca, Sr, Y, Zr, Ag and Cd). Furthermore, some
Ca 10 0.971 16 *
0.914 9 * elements may not be detected (e.g., Al, Co, Si, Sr), as was observed
* s
Cl 60 0.976 6 – 2 – when Ziploc type bags were used.
* *
Cu 20 0.985 26 0.984 25
* *
One of the main contribution of this work that has not been
Fe 10 0.977 29 0.966 21
K 60 0.961 13 *
0.875 9 ** previously reported in the literature (for either handheld or
Mn 30 0.990 22 *
0.980 21 * benchtop XRF instruments), was the use of solid mixtures of CRMs
* *
Mo 180 0.982 16 0.990 11 for the calibration procedure, which increased the number of
*
P 10 0.917 9 0.355 5 ns
* *
available certified standards (without significantly increasing
Pb 60 0.975 22 0.975 21
Rb 10 0.984 4 ***
– 2 – costs) and eliminated hiatus present in some calibration curves.
S 5 0.917 9 *
0.962 4 ***
Finally, results obtained with a limited number of certified and in-
* *
Zn 20 0.966 26 0.961 22 house standards, suggest that it is possible to combine organic and
inorganic matrices for elemental calibrations. Use of larger num-
n¼ number of observations; R¼ correlation coefficient; P ¼ statistical significance.
* bers of (organic and inorganic) CRMs is recommended for future
Pr 0.001.
**
0.001 oP r 0.01. work in this field, especially to increase the operational working
***
0.01 oP r0.05; ns ¼ not significant). linear range of the elements of interest.
 K.G. Mejía-Piña et al. / Talanta 161 (2016) 359–367
Acknowledgments
We thank Jacob Valdivieso-Ojeda for his valuable help in pro-
viding microbial mat samples, and to José Vinicio Macías-Zamora
and Albino Muñoz-Barbosa for contributing with several of the
certified reference materials used in our calibration curves. This
work was supported by Consejo Nacional de Ciencia y Tecnología
(Conacyt) Grant number 154919. One of the authors (K.G.M.P.) was
benefitted by a Ph.D. scholarship granted by Conacyt.
Appendix A. Supplementary material
Supplementary data associated with this article can be found in
the online version at http://dx.doi.org/10.1016/j.talanta.2016.08.
066.
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