Microchemical Journal 168 (2021) 106452

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Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

Microwave induced plasma optical emission spectrometry (MIP OES) and

laser-induced breakdown spectroscopy (LIBS) for multi-element
determination and location in ceramic tableware
Eliézer Quadro Oreste a, b, *, Alexander Ossanes de Souza a, Camila Corrêa Pereira a,
Daisa Hakbart Bonemann a, Mariana Antunes Vieira a, Laiane de Moura Fontes c, Celio Pasquini c,
Anderson Schwingel Ribeiro a
a
Federal University of Pelotas, Center of Chemical, Pharmaceutical and Food Sciences, Postgraduate Program in Chemistry, PO Box 354, 96010-900 Pelotas, RS, Brazil
b
Federal University of Rio Grande, School of Chemical and Food, Postgraduate Program in Technological and Environmental Chemistry, PO Box 474, 96203-900 Rio
Grande, RS, Brazil
c
University of Campinas, Institute of Chemistry, PO Box 6154, 13081-970 Campinas, SP, Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: In the present study, the microwave induced plasma optical emission spectrometry (MIP OES) and laser-induced
Ceramic tableware breakdown spectroscopy (LIBS) complementary techniques are used to determine and locate metals in ceramic
Acid decomposition tableware samples. For quantitative analysis by MIP OES, a new method for sample treatment is proposed,
Analyte localization
preparing the samples using ultrasonic decomposition aided by an acid mixture containing HNO3 and HF. The
Ultrasound
LIBS
highest average concentrations were found in the group of Brazilian samples for most of the analytes. The ac­
MIP OES curacy of the quantitative method was assessed by comparing the results with two methods described in the
literature. No significant differences were detected. Aiming at qualitative analysis and analyte locating by LIBS, a
sample fragment was already sufficient for the analysis, being possible to observe that Al, Ba, Ca, Fe, K, Li, Mg,
Na and Ti are present in the ceramic mass and decorated surface, while Cd, Co, Cr, Cu, Mn, Pb and Zn are found
only on the sample surface. Besides, according to LIBS results, it would be essential to pay attention to
pigmentation, which contains most of the potentially toxic elements, at locations in direct contact with food to
minimize the risk of leaching and avoid human contamination. This study shows that MIP OES and LIBS can be
used complementarily to improve the analytical information used to control the ceramic tableware quality and
safety. The conclusions of this work can be extended to several other types of samples where both the average
contents and the location of the elements are relevant.

1. Introduction
Ceramics are inorganic solids with a crystalline structure containing
metals and non-metals in their composition. These materials have a wide
application in several industrial sectors, of which ceramic tableware
stands out for being present in the daily life of the population for do­
mestic, institutional and promotional use, with food storing as the pri­
mary purpose [1,2].
Ceramic tableware is produced in several countries and has similar
visual characteristics. However, due to the great diversity of raw ma­
terials, these products have different chemical compositions [3,4]. The
final product may contain several chemical elements, which are not
regularly monitored during the production process, resulting in parts not
uniform and more likely to present structural failures. Thus, there is a
possibility that these ceramics contain potentially toxic metals, which
come from the raw material or pigments used in the decorative process
[5,6]. These toxic metals have the potential to be transferred to food,
becoming a risk to consumer health [5,7,8].
Laser-induced breakdown spectroscopy (LIBS) is accredited as an
excellent alternative technique to detect metals in ceramic tableware, as
it is simple, fast and of relatively low operating cost. This technique is
based on the atomization and excitation of the analytes from a laser

* Corresponding author at: Federal University of Pelotas, Center of Chemical, Pharmaceutical and Food Sciences, Postgraduate Program in Chemistry, PO Box 354,
96010-900 Pelotas, RS, Brazil.
E-mail address: eliezerquadro@gmail.com (E.Q. Oreste).

https://doi.org/10.1016/j.microc.2021.106452
Received 14 January 2021; Received in revised form 20 May 2021; Accepted 24 May 2021
Available online 26 May 2021
0026-265X/© 2021 Elsevier B.V. This article is made available under the Elsevier license (http://www.elsevier.com/open-access/userlicense/1.0/).
E.Q. Oreste et al.
pulse focused on the sample, enabling multi-element determinations
applicable to several types of samples, dispensing partially or fully the
samples preparation [9,10]. Also, the microchemical characteristic of
LIBS and its spatial resolution allow probing different parts of the
ceramic tableware, distinguishing between the decorated and non-
decorated features, and locating the detected analytes.
For ceramic samples, the literature reports several works applying
the LIBS technique in archaeological studies. Concerning the determi­
nation of the chemical composition of the ceramic pieces, it is possible to
obtain information about the type of raw material used, the place of
manufacturing, and the processing techniques, which become relevant
indicators about the culture, technology and commercial activities used
by ancient peoples [11–14]. In other studies, this technique is also used
to identify the chemical composition of pigments present on the deco­
rated surface of ceramic pieces [15–17]. Recently, Oreste et al. devel­
oped a simple, fast and efficient method to classify ceramic tableware
commercialized in Brazil manufactured in the country or imported
(predominantly from China) by using the LIBS technique supported by
chemometric methods basing on pattern recognition [18].
In contrast, the use of LIBS for quantitative purpose is more chal­
lenging, showing a high dependence on the sample matrix, which
severely affects the method performance in terms of accuracy and pre­
cision [9,10,19]. For ceramic samples, the difficulty is to obtain cali­
bration solid matrices that reproduce the same characteristics of ceramic
samples. Furthermore, the matrix match could vary for different places
of the same ceramic sample because the overall composition of dyes (for
example) may change from one decoration to another.
On the other hand, for the simultaneous quantitative determination
of the total amount of several elements, other plasma techniques such as
inductively coupled plasma optical emission spectroscopy (ICP OES) and
inductively coupled plasma mass spectrometry (ICP-MS) due to their
sensitivity, accuracy and precision, rendering numerous applications
[20]. Recently, the interest in the technique of microwave induced
plasma optical emission spectrometry (MIP OES) is increasing, making it
an excellent alternative to the plasma techniques mentioned above. The
MIP OES is based on a microwave generator to produce and sustain the
plasma supplied with nitrogen gas, where elements are excited. The
technique is safe and low-cost due to the replacement of flammable or
expensive gases, as nitrogen can be easily obtained from atmospheric air
[21,22]. In MIP OES, the sample solutions are conventionally introduced
using a nebulization system. An alternative to the sample preparation
step is acid decomposition that can be applied to different types of
samples [23]. However, ceramics are considered complex samples
because they have a high silicon content in their composition, which
requires different conditions for their preparation, such as hydrofluoric
acid [20,24]. Recently, Müller et al. [25] applied acid decomposition
and extraction methods to prepare mineral fertilizer samples to deter­
mine 19 elements using the MIP OES technique. Other studies also
report using this technique to determine different analytes in mineral
matrices [26–28].
Ceramic samples can be prepared from acid decomposition using
microwaves [20] which has the advantages of the short time required for
preparation, requires small volumes of concentrated acid, low analytical
blanks and residual carbon content. However, its main disadvantage is
the high cost attributed to the ovens. The use of ultrasound in the
preparation of samples is an excellent alternative. It has some advan­
tages concerning microwaves, such as simplicity, low cost, the possi­
bility of using a larger quantity of samples and does not require special
adaptation for the reaction flask [29].
Therefore, both analytical techniques LIBS and MIP OES show
complementary characteristics. Improvement of the analytical infor­
mation can be achieved by combining the results of these techniques, as
demonstrated in this work.
No study was found in the literature involving LIBS and MIP OES as
complementary techniques for multi-element analysis. Thus, consid­
ering the relevance of knowing the distribution and concentration of
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Microchemical Journal 168 (2021) 106452
metals in ceramic tableware, the objective of the present study is to use
both techniques for the determination of sixteen analytes in samples of
ceramic tableware manufactured in Brazil and imported.
2. Experimental
2.1. Laser-induced breakdown spectroscopy
The LIBS instrument used in this work is similar to that described by
Cortez and Pasquini [30] and previously employed by Oreste et al. [18]
in ceramic tableware analysis. Thus, a Nd:YAG pulsed laser with a
fundamental wavelength of 1064 nm (Quantel, Brio) was used, with a
pulse rate of 20 Hz, pulse duration of 5.5 ns and pulse energy 50 mJ. The
laser beam is reflected by a dichroic mirror (Ealing Electron-Optics)
positioned at 45◦ and then is focused on the sample through a lens 10
cm focal length calcium fluoride (Ealing Electron-Optics). The distance
between the focusing lens and the sample was fixed at 9.6 cm to avoid
air breakdown.
The radiation emitted from the micro-plasma generated by the laser
pulse is collected by a lens and focused on the entrance of an optical fibre
with a 100 µm internal diameter and operating spectral range between
160 and 1200 nm, which is responsible for the transport from this ra­
diation to an echelle polychromator (Mechelle 5000, Andor Technol­
ogy). The emission spectrum is then acquired through an intensified
charge-coupled device (ICCD) camera with 1024 × 1024 pixels (iStar
DH 734, Andor Technology) and stored in a microcomputer. The spec­
tral range obtained is from 200 to 900 nm with a resolution of 0.04 nm.
For the analysis of ceramic tableware samples by LIBS, the delay and
integration time of 1 µs were used, in addition to an accumulation of five
pulses in five different locations (25 pulses in total) for the generation of
each representative spectrum, in order to obtain the analytical signals
used for later interpretations. The ceramic fragments analyzed were
placed on a soft sponge and under a platform, containing a central hole
approximately 5 mm × 10 mm in size. This system is necessary to
facilitate the control of the sample to focusing lens distance since the
samples had different thicknesses.
In the interpretation of LIBS results, the number of lines used to
identify the analytes is related to the emission features found in the
spectra. Table S1 shows the determined analytes and the wavelengths
for the emission lines evaluated in the present study extracted from the
atomic spectra database of the National Institute of Standards and
Technology (NIST) [31].
2.2. Scanning electron microscopy (SEM)
A scanning electron microscope model J6360 LV (Joel, Japan) was
used to assess the profile of the craters formed on the samples surface
after the accumulation of laser pulses in the LIBS analysis. The samples
were fixed on aluminium support using a double-sided conductive tape
and coated with a gold layer using a Bal-Tec metallization system, model
MD20.
2.3. Microwave induced plasma optical emission spectrometry
A MIP OES model 4200 (Agilent Technologies, Australia) was used
for quantitative multi-element determinations, equipped with an One­
Neb nebulizer, a peristaltic pump, and a PTFE cyclonic nebulizer
chamber which is tolerant to the introduction of solutions containing
hydrofluoric acid. The plasma was sustained with nitrogen gas from
atmospheric air, obtained through a nitrogen generator model 4107
(Agilent Technologies, Australia), with flow rates of 20 and 1.5 L min− 1
for the plasma and auxiliary gas, respectively.
The solutions resulting from the ceramic sample treatment were
aspirated for 15 s, followed by a plasma stabilization for another 15 s. All
measurements were performed in triplicate with an integration time of
3 s. The background signals were corrected automatically by subtracting
E.Q. Oreste et al.
the spectra of a blank from that of the sample. Other operating param­
eters are shown in Table S2.
The concentrations of some analytes obtained by the MIP OES
technique were used in an exploratory analysis by principal components
(PCA). Thus, it was possible to evaluate the feasibility of separation
between groups of Brazilian and imported ceramic tableware samples.
This chemometric treatment was conducted using the Unscrambler 11.0
software (CAMO, Norway).
2.4. Materials and reagents
The reagents used in this study were of analytical grade, and all so­
lutions were prepared with deionized water, obtained from a glass
distillation system, model MA078/5 (Marconi, Brazil) and, subse­
quently, eluted in a deionizer model CS1800 Evolution (Permution,
Brazil). The calibration solutions for the MIP OES analyzes were pre­
pared in HNO3 5% v/v, from the dilution of a number 6 multi-element
stock solution for ICP (Sigma Aldrich, Germany) containing 100 mg
L− 1 for all investigated analytes.
For the preparation of the samples, HNO3 65% w/w (Vetec, Brazil),
bidistilled below its boiling point in a quartz distiller model MA-075
(Marconi, Brazil), was used. In this step, HF 40% w/w (Vetec, Brazil)
also was employed.
All materials used to prepare the solutions, standards and sample
decomposition were washed with water and detergent, immersed in an
HNO3 10% v/v solution for 48 h, washed with deionized water and dried
at room temperature before use.
2.5. Sample preparation procedure
One hundred samples of ceramic tableware were analyzed by MIP
OES and LIBS, including mugs, cups, bottles of spices, toothpick holder,
plates, teapots, bowls, dishes, pots and casseroles. The samples were
acquired in the local market of Pelotas/RS and Campinas/SP. Fifty
ceramic tableware were manufactured in Brazil, and the other fifty were
imported from abroad (mostly produced in China).
All samples were previously washed and dried before being frag­
mented. For the analyzes using the LIBS technique, it was not necessary
a rigorous preparation of the ceramic samples, only the selection of a
small solid fragment preferably containing a flat surface.
For MIP OES analysis, all samples were submitted a preliminary
treatment, being fragmented and comminuted through a ball mill,
model MM 400 (Retsch, Germany), for 5 min at a vibration frequency of
15 Hz. Then, the samples were sieved in a shaking system (A Bronzinox,
Brazil) for 20 min at a frequency of 5 Hz to obtain particles with particle
sizes ranging from > 150 µm (100 mesh) to < 25 µm (500 mesh). Finally,
all of these samples were submitted to the acidic decomposition pro­
cedure in an ultrasonic bath model Elmasonic S 40H (Elma, Germany),
with a power of 560 W and a frequency of 37 kHz. For comparative
purpose, four samples (2 Brazilian and two imported) were also pre­
pared by two other acid decomposition methods already described in the
literature: one in an open system and the other in a closed system, for
which a digester block was used, model MA 850 (Marconi, Brazil). The
three procedures used are described below.
LIBS probed the same piece of ceramic or similar to the one ground
and submitted to the digestion procedure aiming at the analysis by MIP
OES since the main objective of sampling was selecting ceramic frag­
ments that included mass and all the surface colours.
2.5.1. Acid decomposition by ultrasonic irradiation (US)
This decomposition method is identical to that described by Oreste
et al. [32]. Approximately 25 mg of sample (particle size < 25 µm) were
weighed directly in volumetric polypropylene (PP) flasks and, subse­
quently, an acidic mixture containing 0.5 mL of HNO3 65% w/w and 0.5
mL of HF 40% w/w was added. The solutions were placed in an ultra­
sonic bath, remaining for two hours at a temperature of 40 ◦ C, which
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Microchemical Journal 168 (2021) 106452
was directly controlled by the equipment. After that period, the resulting
solutions were clear, and the final volume of 20 mL was completed with
deionized water. Thus, the final solutions showed theoretical acidity of
5% v/v due to HNO3 and HF added.
2.5.2. Acid decomposition in an open system (OS)
This acid decomposition method was adapted from the procedure
described by Santos et al. [33]. Therefore, approximately 100 mg of
sample (particle size < 25 µm) were weighed directly in PTFE flasks,
and, subsequently, an acid mixture containing 3 mL of HNO3 and 1 mL of
HF was added. The open flasks were placed directly to a digester block
heated to a temperature of 150 ◦ C, remaining until almost complete
vaporization of the acids. After cooling to room temperature, the solu­
tion was transferred to volumetric flasks of PP, and the volume of 30 mL
was completed with deionized water.
2.5.3. Acid decomposition in a closed system (CS)
For acid decomposition in a closed system, the procedure described
in method 3052 of the Environmental Protection Agency (EPA) [34] was
followed, replacing the microwave oven with the digester block.
Approximately 250 mg of sample (particle size < 25 µm) were weighed
directly in the bottles made of PTFE, and an acidic mixture containing 9
mL of HNO3 and 3 mL of HF was added. Then, the flasks were closed and
placed in a digester block, where they remained for three hours at a
temperature of 120 ◦ C. The bottles were opened after their complete
cooling, ensuring safety. The obtained solutions were transferred to
volumetric PP flasks, and the volume was made to 40 mL with deionized
water.
Except for the method proposed by US, all samples were diluted due
to the 5% v/v acidity content maximum limitation for the introduction
of samples in analyzes by MIP OES.
3. Results and discussion
3.1. Effect of the accumulation of laser pulses in LIBS
A fragment of the ceramic tableware was placed on the sample
holder, and the laser was focused on its surface. Four average emission
spectra were obtained by accumulating 1, 5, 10 and 15 laser pulses in
five different regions of the sample (totalizing 5, 25, 50 and 75 pulses,
respectively). Thus, it was possible to evaluate the intensity of the an­
alyte emission signals as a function of the number of accumulated pulses.
According to this study, it was possible to observe that the intensity of
the emission signals from a total of up to five laser pulses is very low,
making it challenging to identify some analytes. From a total of 25
pulses, it is already possible to distinguish the atomic emission peaks of
the analytes. Therefore, in the present study, five laser pulses accumu­
lating in five different sample regions were adopted. Despite the increase
in the intensity of the emission analytes peaks, a higher number of pulses
was not employed due to a large increase in the background emission,
making it challenging to identify analytes present in lower
concentrations.
Under the condition established in this study, the sensitivity of the
integrated LIBS signals allowed the identification of most of the ele­
ments detected by MIP OES analysis of the ceramic samples. The ele­
ments Cd and Pb, for example, are present in low concentration in
several ceramic samples, as determined by MIP OES. Nevertheless, they
are easily detected and located by LIBS, as shown in Fig. 1. It is worth
reminding that LIBS assess the analytes directly on the ceramic surface,
where they are present in a substantially higher concentration than the
average concentration of the whole sample.
Typical sections of LIBS spectra and some relevant characteristic
emission features obtained by probing the mass, the surface, and a
decorated portion of an imported ceramic sample, are depicted in Fig. 1.
The SEM technique was used to evaluate the crater profile formed
from the accumulation of laser pulses in a specific sample region. In
E.Q. Oreste et al. Microchemical Journal 168 (2021) 106452

Fig. 1. Emission spectrum obtained by LIBS with emphasis on the spectral range of (A) 278–282 nm, (B) 355–365 nm, (C) 366–378 nm and (D) 392–299 nm.
Analysis of fragments of imported ceramic tableware to identify analytes in different regions: (E) ceramic mass, (F) yellow surface, (G) white surface, (H) black
surface and (I) red surface.

Fig. 2. A purple pigmented surface of ceramic tableware after analysis by LIBS. (A) Image of a ceramic fragment containing several sampling points; Image obtained
by SEM after the incidence of (B) 1 laser pulse and (C) 5 laser pulses.

Fig. 2, it is possible to verify a more extensive sampling of the ceramic
surface in the region with a large number of accumulated laser pulses,
which resulted in spectra with more intense signals.
3.2. Multi-element quantification and location in samples of ceramic
tableware by MIP OES and LIBS
The LIBS technique was used to identify the presence of the analytes
in the internal mass and surface (usually decorated) of ceramic table­
ware. Most of the samples have their surface decorated with different

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E.Q. Oreste et al. Microchemical Journal 168 (2021) 106452

colours and, from this study, it was possible to determine the elements Table 2
present in each pigment only by aiming the laser pulses onto the region Results of concentration of different analytes as determined by MIP OES in
of interest, requiring a minimal manipulation of the samples. ceramic tableware manufactured in Brazil, prepared from different acid
The results obtained in the qualitative multi-element determinations decomposition methods (n = 3).
by LIBS are presented in Figs. S1–S4, which relate the number of samples Analyte Concentration, x ± sd (RSD, %), in mg g− 1
or *µg g− 1

(in percentage) with each sample region (internal mass or external

Sample Brazilian Ceramic 1 Sample Brazilian Ceramic 2
surface) in the determination of Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg,
Mn, Na, Pb, Ti and Zn. The evaluation of the distribution of analytes by US OS CS US OS CS

LIBS was related to the quantitative results obtained by the MIP OES Al 88.4 ± 91.5 ± 90.3 ± 138 ± 6 137 ± 1 139 ± 4
technique, making it possible to associate each sample region with the 2.9 (3.3) 2.0 (2.2) 1.1 (1.2) (4.3) (0.7) (2.9)
Ba* 574 ± 579 ± 581 ±
most significant contribution to the concentration of the analytes stud­ < < <
LOQ(M) LOQ(M) LOQ(M) 20 (3.5) 29 (5.0) 19 (3.3)
ied, as described below. Ca 1.6 ± 1.6 ± 1.6 ± 21.7 ± 22.0 ± 21.7 ±
Through MIP OES analysis, the concentrations of the same analytes 0.1 (6.2) 0.1 (6.2) 0.2 1.3 (6.0) 0.3 (1.4) 2.3
were obtained after an acidic decomposition of samples by ultrasonic (12.5) (10.6)
irradiation. Table 1 shows the figures of merit. The analytical curves Cd* 21,7 ± 21,0 ± 21,9 ± < < <
0,4 (1,8) 0,9 (4,3) 0,8 (3,6) LOQ(M) LOQ(M) LOQ(M)
were established in the range 0.5 – 5.0 mg L− 1 for all analytes, except for Co* < < < 16.0 ± 16.2 ± 15.9 ±
Li (the maximum concentration used was 2.0 mg L− 1). This concentra­ LOQ(M) LOQ(M) LOQ(M) 0.2 (1.2) 0.1 (0.6) 0.8 (5.0)
tion range is equivalent to 0.4–4.0 mg g− 1 (1.6 mg g− 1 for Li) in the Cr* < < < < < <
original sample, considering the treatment by US method and final LOQ(M) LOQ(M) LOQ(M) LOQ(M) LOQ(M) LOQ(M)
Cu* 23.5 ± 23.1 ± 23.9 ±
dilution of the dissolved sample. The lowest LOQ(M) were obtained for < < <
LOQ(M) LOQ(M) LOQ(M) 0.3 (1.3) 0.6 (2.6) 0.7 (2.9)
Ba, Cr, Li, Mg and Mn (lower than one µg g− 1). The majority of analytes Fe 3.5 ± 3.3 ± 3.2 ± 3.7 ± 3.5 ± 3.5 ±
showed LOQ(M) between 1 and 10 µg g− 1, except for Pb and Zn, for 0.1 (2.8) 0.2 (6.1) 0.3 (9.4) 0.2 (5.4) 0.1 (2.8) 0.2 (5.7)
which the values are 13 and 22 µg g− 1, respectively. Also, for all ana­ K 21.2 ± 22.8 ± 21.8 ± 14.7 ± 14.0 ± 14.2 ±
lytes, the analytical curves showed an R2 ≥ 0.996. 1.1 (5.2) 3.0 1.1 (5.0) 0.8 (5.4) 2.5 0.4 (2.8)
(13.2) (17.8)
The accuracy of the acid decomposition results using ultrasonic Li* 47.1 ± 47.2 ± 47.3 ± 54.9 ± 56.5 ± 55.8 ±
irradiation was evaluated by comparing two other methods (OS and CS). 0.1 (0.2) 0.2 (0.4) 0.3 (0.6) 6.4 3.6 (6.4) 1.7 (3.0)
The results obtained for this study are shown in Tables 2 and 3, which (11.6)
refer to samples of ceramic tableware manufactures in Brazilian and Mg 5.4 ± 5.5 ± 5.4 ± 5.8 ± 5.7 ± 5.8 ±
0.2 (3.7) 0.1 (1.8) 0.3 (5.6) 0.1 (1,7) 0.1 (1.7) 0.1 (1.7)
abroad, respectively.
Mn* 259 ± 264 ± 253 ± 219 ± 8 220 ± 1 219 ± 9
According to Tables 2 and 3, some elements showed concentrations 16 (6.2) 18 (6.8) 39 (3.6) (0.4) (4.1)
lower than the LOQs in several samples and could not be quantified by (15.4)
the methods of sample preparation and analytical technique used. Na 6.8 ± 6.8 ± 6.8 ± 8.6 ± 8.6 ± 8.7 ±
However, all elements had measurable concentrations in at least one 0.7 0.3 (4.4) 0.1 (1.5) 0.3 (3.5) 0.5 (5.8) 0.4 (4.6)
(10.3)
sample (as for Cd), making it possible to assess the accuracy of the Pb* 305 ± 347 ± 350 ± 107 ± 2 112 ± 6 109 ± 3
proposed method for multi-element determination of all elements by 16 (5.2) 51 56 (1.9) (5.4) (2.7)
MIP OES. (14.7) (16.0)
The results obtained by the different sample preparation methods are Ti* 230 ± 8 226 ± 226 ± 381 ± 6 384 ± 3 391 ±
(3.5) 12 (5.3) 16 (7.1) (1.6) (0.8) 12 (3.1)
statistically equivalent, according to the evaluation using the paired t-
Zn* 50.9 ± 50.2 ± 47.8 ± 121 ± 125 ± 116 ± 6
test at 95% confidence limit. Thus, the proposed method of acid 54 6.0 2.4 (5.0) 15 10 (8.0) (5.2)
decomposition with ultrasound can be securely applied to analyze (10.6) (12.0) (12.4)
samples of ceramic tableware by MIP OES since it showed accuracy
x: average; sd: standard deviation; RSD: relative standard deviation; US: acid
compared to other reference methods. The US proposed method of decomposition by ultrasonic irradiation; OS: acid decomposition in an open
preparation proved to be slightly more precise than the other methods system; CS: acid decomposition in a closed system; < LOQ(M): below the quan­
evaluated since it presented a lower mean RSD value (equivalent to tification limit of the method.

4.9%), whereas, for the OS and CS methods, this value was 5.3 and 5.9%,
Table 1 respectively.
Figures of merit obtained for multi-element determination in samples of ceramic Considering the sample throughput, the proposed method (US) has
tableware by MIP OES.
greater capacity than the other methods, as the samples are prepared in
Analyte Slope (L mg− 1) R2 LOD(M) (µg g− 1) LOQ(M) (µg g− 1) PP bottles and placed directly in an ultrasonic bath. During the prepa­
Al 41,149 0.996 0.5 1.6 ration time (two hours), it was possible to process twelve replicates
Ba 393,021 0.999 0.2 0.5 simultaneously using this method. Thus, with larger ultrasonic baths, it
Ca 584,287 0.999 1.0 3.5 is possible to prepare a larger number of samples. The other preparation
Cd 32,196 0.999 1.3 4.5
methods (OS and CS) require larger bottles of PTFE and digester block or
Co 14,920 0.999 2.6 8.8
Cr 55,958 0.999 0.1 0.4 heating plate, resulting in less processing capacity (six replicates) during
Cu 193,554 0.999 0.8 2.8 the preparation period previously described.
Fe 13,902 0.999 1.7 5.8 The method proposed was applied to the other samples of ceramic
K 92,109 0.998 1.5 4.9 tableware manufactures in Brazilian and abroad. The concentration
Li 1,758,393 0.999 0.01 0.04
Mg 257,206 0.999 0.2 0.6
results obtained by the MIP OES are shown in Figs. S5–S8. The average
Mn 49,077 0.999 0.1 0.3 concentration was calculated for all samples that presented concentra­
Na 426,132 0.998 2.2 7.2 tions higher than the LOQ(M), obtaining an average value for each
Pb 5158 0.998 4.0 13.4 ceramic tableware group (Brazilian and imported), as shown in Table 4.
Ti 51,505 0.999 2.8 9.5
According to the average concentrations of Al obtained, this element
Zn 21,054 0.998 6.5 21.7
is present in a similar concentration in the two sample groups. Ca and Na
R2: Linear squared correlation coefficient; LOD(M): Limit of detection of the are present in higher concentration in the Brazilian samples. In contrast,
method; LOQ(M): Limit of quantification of the method.

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E.Q. Oreste et al. Microchemical Journal 168 (2021) 106452

Table 3 Table 4
Results of concentration of different analytes by MIP OES in ceramic tableware Average concentrations of Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Pb, Ti
manufactured abroad, prepared from different acid decomposition methods (n and Zn obtained by MIP OES from samples of ceramic tableware manufactured
= 3). in Brazil and imported.
1 1 1
Analyte Concentration, x ± sd (RSD, %), in mg g− or *µg g− Analyte Concentration, x ± sd, in mg g− or Difference between samples
*µg g− 1 groups (%)
Sample Imported Ceramic 1 Sample Imported Ceramic 2
Brazilian Imported
US OS CS US OS CS
Ceramics Ceramics
Al 142 ± 4 141 ± 4 142 ± 1 121 ± 8 121 ± 5 121 ± 6
Al 84.6 ± 28.1 83.6 ± 24.8 1.2
(2.8) (2.8) (0.7) (6.6) (4.1) (5.0)
Ba 2.7 ± 4.6 1.9 ± 1.6 29.4
Ba 1.7 ± 1.7 ± 1.6 ± 3.4 ± 3.4 ± 3.3 ±
Ca 14.1 ± 5.8 9.4 ± 13.9 32.9
0.1 (5.9) 0.1 (5.9) 0.2 0.1 (2.9) 0.1 (2.9) 0.2 (6.1)
Cd* 58.9 ± 53.9 57.5 ± 41.2 2.4
(12.5)
Co* 258.4 ± 229.2 150.1 ± 71.6 41.9
Ca 10.3 ± 10.3 ± 10.0 ± 6.1 ± 5.9 ± 6.0 ±
Cr* 101.3 ± 223.6 75.8 ± 106.4 25.2
0.5 (4.8) 0.2 (1.9) 1.2 0.2 (3.3) 0.1 (1.7) 0.1 (1.7)
Cu* 19.2 ± 14.1 23.9 ± 14.1 19.5
(12.0)
Fe 3.8 ± 1.6 4.6 ± 2.4 16.1
Cd* < < < < < <
K 11.7 ± 3.9 16.8 ± 6.9 30.7
LOQ(M) LOQ(M) LOQ(M) LOQ(M) LOQ(M) LOQ(M)
Li* 38.7 ± 20.6 127.1 ± 145.5 69.5
Co* 80.0 ± 78.6 ± 86.0 ± 397 ± 393 ± 385 ±
Mg 7.7 ± 4.5 16.0 ± 35.4 51.7
6.5 (8.1) 5.9 (7.5) 4.4 (5.1) 14 (3.5) 35 (8.9) 29 (7.5)
Mn* 243.1 ± 283.2 399.2 ± 198.1 39.1
Cr* 39.4 ± 39.0 ± 39.5 ± 163 ± 9 163 ± 7 164 ± 5
Na 19.9 ± 26.4 11.1 ± 5.8 44.3
1.2 (3.0) 2.6 (6.7) 1.2 (3.0) (5.5) (4.3) (3.0)
Pb* 739.3 ± 1157.4 872.0 ± 1082.6 15.2
Cu* 19.8 ± 19.4 ± 19.1 ± 31.5 ± 31.6 ± 31.8 ±
Ti* 1067.5 ± 893.5 841.2 ± 936.3 21.2
1.6 (8.1) 2.2 2.7 0.3 (1.0) 0.3 (0.9) 0.8 (2.5)
Zn* 1370.2 ± 956.5 ± 756.6 30.2
(11.3) (14.1)
1274.4
Fe 3.4 ± 3.6 ± 3.0 ± 9.9 ± 9.9 ± 9.9 ±
0.4 0.4 0.2 (6.7) 0.6 (6.1) 0.5 (5.0) 0.3 (3.0) x: average; sd: standard deviation.
(11.8) (11.1)
K 11.5 ± 11.3 ± 11.5 ± 8.5 ± 8.7 ± 8.8 ±
0.9 (7.8) 0.3 (2.6) 0.6 (5.2) 0.1 (1.2) 0.4 (4.6) 0.3 (3.4) Manganese is found in the highest average concentration in imported
Li* 880 ± 880 ± 899 ± 47.2 ± 47.4 ± 47.8 ± samples, emphasising those containing black color on its surface. The
24 (2.7) 56 (6.4) 119 0.4 (0.8) 0.5 (1.0) 1.5 (3.1) LIBS results indicate the presence of this analyte in some colors on the
(13.2)
surface of the samples, characterizing this analyte as a pigment. The
Mg 3.6 ± 3.5 ± 3.6 ± 31.1 ± 31.6 ± 31.5 ±
0.1 (2.8) 0.1 (2.8) 0.1 (2.8) 1.2 (3.8) 0.5 (1.6) 2.4 (7.6)
literature reports that this element is from MnO and is part of the
Mn < < < 529 ± 522 ± 6 525 ± 4 chemical composition of black pigments [11,15,43], corroborating the
LOQ(M) LOQ(M) LOQ(M) 10 (1.9) (1.1) (0.8) results found in this study. The analytes Cu, Co and Cr, were also
Na 4.2 ± 4.2 ± 4.2 ± 4.6 ± 4.7 ± 4.6 ± identified only in some colors on the surface of ceramic tableware, as
0.4 (9.5) 0.1 (2.4) 0.3 (7.1) 0.1 (2.2) 0.5 0.2 (4.3)
they are derived from pigments used in decoration. Copper can come
(10.6)
Pb* 63.5 ± 60.8 ± 62.4 ± 105 ± 8 104 ± 103 ± from acetates, oxides, carbonates, phosphates and other additives, while
4.2 (6.6) 8.3 4.5 (7.2) (7.6) 20 12 Co is originated mainly from oxides and aluminates [15,41,44,45]. The
(11.5) (19.2) (11.6) analyte Cr is originated from chromates, which are part of the chemical
Ti 2.9 ± 3.0 ± 3.0 ± 3.4 ± 3.3 ± 3.5 ±
composition of several types of pigments required by the ceramic in­
0.3 0.1 (3.3) 0.1 (3.3) 0.1 (2.9) 0.3 (9.1) 0.5
(10.3) (14.3)
dustry due to their chemical and thermal stability [15,41,46,47].
Zn* 992 ± 979 ± 971 ± 284 ± 9 286 ± 8 290 ± 8 Cadmium was quantified only in 21 samples due it is present at a
45 (4.5) 24 (2.4) 136 (3.2) (2.8) (2.8) concentration below the quantification limit of the MIP OES in the
(14.0) remaining samples. This analyte was identified in some colorations on
x: average; sd: standard deviation; RSD: relative standard deviation; US: acid the surface of the ceramic tableware by LIBS but in a larger number of
decomposition by ultrasonic irradiation; OS: acid decomposition in an open samples than the analysis by MIP OES. Unlike for MIP OES technique,
system; CS: acid decomposition in a closed system; < LOQ(M): below the quan­ LIBS analysis can be carried out directly on the solid sample without
tification limit of the method. requiring sample preparation by acid decomposition and, consequently,
not undergoing the effect of the analyte dilution. The presence of Cd was
the highest average concentrations of Mg and K are found in the im­ identified in decorated parts of yellow, orange, red, and brown, in
ported samples. These five analytes present in the range concentration of agreement with previous studies published in the literature [11,15,48].
mg g− 1 were also detected by LIBS, being present in all samples and About Pb, imported ceramics presented a higher average concen­
sampling points (mass and surface). These analytes have their origin in tration compared to Brazilian samples. According to LIBS results, Pb was
the raw material and fluxing agent used for ceramic manufacturing identified at all sampling points on the surface, but the characteristic
[35–37]. emission features show lower intensities in the white regions. Lead can
For Li, the imported samples presented higher concentration ac­ originate from fluxing agents used in the preparation of enamels, such as
cording to the MIP OES results. LIBS identified this analyte in the mass PbO. Besides, it can also be present in several pigments, in the form of
and surface of practically all samples, which originated from a fluxing chromate, sulfate, carbonate, among others [11,15,17,39,44]. The
agent used in the manufacture of masses or enamels [37,38]. The ana­ presence of toxic elements such as Cd and Pb requires attention since
lytes Ba and Ti were also identified in all sampling regions, while Zn was several works mention the possibility of leaching ceramic tableware
determined only on the surface of ceramic tableware, according to the elements to food, potentially causing damage to human health [7,8,49].
results obtained by LIBS. These analytes are from raw materials used in
the manufacture of mass and enamels, such as BaCO3, ZnO and TiO2 3.3. Exploratory principal component analysis (PCA) based on the
[36,37,39,40]. Concerning Fe, the highest average concentration is concentration of the elements determined by MIP OES
found in imported ceramics, identified by LIBS at all sampling points,
but with a lower occurrence in white regions located on the surface, as The concentrations of Al, Ca, Na, Mg, and K might be appropriate to
expected [41]. This element can be present in the formulation of several be submitted to a PCA of the sample set, aiming to identify the presence
pigments, mainly as oxides [15,42]. of clusters. Fig. S9A shows the scores plot for the first two principal

6
E.Q. Oreste et al.
components of the PCA conducted on the whole set of samples. Together
these components explain 80% of the variance of the data set. Three
main groups may be identified. One group of 89 samples contains most
of the imported and Brazilian samples. The other groups were identified,
one for imported (six samples) and the other for Brazilian samples (five
samples). These groups of imported and Brazilian samples are distin­
guished from the main group as a function of their higher content of Mg
and Na, respectively, according to the loadings plot shown in Fig. S9B.
The small group of Brazilian samples identified in the previous PCA
has a high Na content, much higher than the average. These ceramic
tableware samples are supplied by the same manufacturer and possibly
were produced with the same raw material (e.g., sodium feldspar). The
other group, containing five imported samples, has a higher Mg content,
indicating the use of a less common raw material compared with the
majority of the imported samples.
Additional PCA was carried out using the group of 89 samples
detected by the first PCA. The results show another group of four im­
ported ceramics distinguished from the remaining samples due to the
unusually high content of Ca found in these samples. After excluding this
group, a final PCA was conducted with the remaining 85 samples, and
clear separation in the second and third PC was obtained between the
group of imported and Brazilian ceramics with few samples. The asso­
ciated principal component loadings of the variables show that the
concentrations of Ca and K contribute mostly to grouping. The average
values for Ca and K of the 85 samples evidence the differences between
the two samples groups with values of 13.3 and 3.8 mg g− 1 of Ca and
12.0 and 17.9 mg g− 1 of K for the Brazilian made and imported samples
Fig. 3. Plots of (A) scores and (B) loadings obtained by PCA of the concentration of Ca and K determined by MIP OES in 85 ceramic tableware samples. Brazilian
(blue points); imported samples (red points).
7
Microchemical Journal 168 (2021) 106452
respectively.
Finally, a PCA was conducted using only the concentrations of Ca
and K, and the separation between the samples manufactured in Brazil
and imported was attained, with 7 imported samples classified as Bra­
zilians. Only one made in Brazil classified in the imported group, as
shown in Fig. 3A and 3B. Considering the exploratory results for ceramic
tableware classification, it is possible to conclude that only the con­
centrations of Ca and K determined by MIP OES are required for effec­
tive classification of the sample origin.
In a previous study by Oreste et al. [18] ceramic tableware was
classified as Brazilian or imported based on LIBS analysis and the use of
chemometrics. Among several elements detected, Al and Ca contributed
mostly to the separation of the sample groups. In the present study, these
analytes showed higher mean concentrations and emission intensities,
obtained by MIP OES and LIBS, respectively, for the group of Brazilian
samples, in agreement with the results reported by Oreste et al. [18].
However, for Al, there is no significant difference between the two
groups of samples, which can be explained by the mode of sampling,
since the entire sample was used in the analyzes by MIP OES, while in
the study previously reported, the analyzes were made only on the
ceramic mass surface [18]. In fact, in the present study, Al does not
affect distinguishing the sample origin. The fact that K contributes
significantly to sample classification in the present work may also be
attributed to the different sampling mode used in LIBS and MIP OES.
E.Q. Oreste et al.
4. Conclusions
The MIP OES technique show advantages such as simplicity, speed
and lower operating cost, being possible the quantitative determination
of the analytes in samples of ceramic tableware. The proposed digestion
method associated with the elemental determination using MIP OES,
though requiring the sample to be finely ground and the use of
concentrated acids, allows the use of milder conditions, imparts safety,
and demands low-cost equipment.
The concentrations of macroelements Ca, Al, Na, K and Mg deter­
mined by MIP OES can be used to distinguish between ceramic table­
ware imported from those made in Brazil. The results partially agree
with previous work where the classification using only the analytical
information supplied by LIBS was employed. The concentrations deter­
mined by MIP OES of the elements Ca and K are found sufficient to
classify the samples tableware as made in Brazil or imported.
According to results obtained by LIBS, it is possible to assess quali­
tatively the distribution of metals present in the samples of ceramic
tableware manufactured in Brazil and imported. Most of the analytes
were present in both parts analyzed (internal ceramic mass and external
decorated surface). However, some analytes (Cd, Co, Cr, Cu, Mn, Pb and
Zn) were present only on the external surface of ceramic tableware, a
characteristic of elements present in the pigments used for decoration.
Thus, the control of tableware composition is urgent to ensure its quality
and safety, especially for Cd and Pb, that are potentially toxic and can be
transferred to food when subjected to different conditions, such as
heating (in microwaves, for example) or in contact with acidic pH foods.
The results obtained in this work show the relevance of monitoring
metals in ceramic tableware, alerting the regulatory agencies for the
potential hazard to the consumers due to potentially toxic elements.
Combining the results obtained from both techniques confirms their
complementary characteristics, allowing them to improve the quality of
the analytical information about the sample. The advantages of joining
MIP OES and LIBS can be extended to several other types of samples
matrices.
CRediT authorship contribution statement
Eliézer Quadro Oreste: Conceptualization, Methodology, Valida­
tion, Formal analysis, Investigation, Writing - original draft. Alexander
Ossanes de Souza: Methodology, Validation, Formal analysis, Writing -
original draft. Camila Corrêa Pereira: Methodology, Validation,
Formal analysis, Writing - original draft. Daisa Hakbart Bonemann:
Methodology, Validation, Formal analysis, Writing - original draft.
Mariana Antunes Vieira: Validation, Resources, Writing - review &
editing, Visualization, Supervision, Funding acquisition. Laiane de
Moura Fontes: Methodology, Validation, Formal analysis. Celio Pas­
quini: Conceptualization, Validation, Formal analysis, Resources,
Writing - review & editing, Visualization, Supervision, Funding acqui­
sition. Anderson Schwingel Ribeiro: Conceptualization, Validation,
Resources, Writing - review & editing, Visualization, Supervision,
Project administration, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The authors are grateful to Instituto Nacional de Ciências e Tecno­
logias Analíticas Avançadas (INCTAA), processes FAPESP 2014/50951-
4 and CNPq 465768/2014-8, to Agência Nacional de Vigilância
Sanitária (ANVISA) through the MCTI/CNPq/ANVISA 23/2012, process
403403/2012-0, for financial support. This study was financed in part
8
Microchemical Journal 168 (2021) 106452
by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior -
Brasil (CAPES) - Finance Code 001, and Fundação de Amparo à Pesquisa
do Estado do Rio Grande do Sul (FAPERGS) for scholarship support.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.microc.2021.106452.
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