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Nuclear Inst.

and Methods in Physics Research B 477 (2020) 150–153

Contents lists available at ScienceDirect

Nuclear Inst. and Methods in Physics Research B


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

Signature of the Himalayan salt T


a a,b a a,b a,b a,b,⁎
T. Kuhn , P. Chytry , G.M.S. Souza , D.V. Bauer , L. Amaral , J.F. Dias
a
Ion Implantation Laboratory, Institute of Physics, Federal University of Rio Grande do Sul, Av. Bento Gonçalves 9500, P.O. Box 15051, CEP 91501-970 Porto Alegre, RS,
Brazil
b
Graduate Program on Materials Science, Federal University of Rio Grande do Sul, Av. Bento Gonçalves 9500, CEP 91540-000 Porto Alegre, RS, Brazil

ABSTRACT

Sodium chloride (NaCl) is the most important seasoning in every table around the world. Despite refined table salt is the most popular type of salt, the pinkish salt
known as Himalayan salt is gaining importance worldwide.
The aim of the present work is to measure the elemental content of different salts sold in the Brazilian market and compare them with Himalayan salt. To that end,
PIXE (Particle-Induced X-ray Emission) was used to characterize salt samples. The experiments employed 2 MeV protons with typical currents of 0.5 nA at the target.
X-rays were detected by a Si(Li) detector placed at 135° with respect to the beam direction.
The results indicate that besides Na and Cl, Brazilian salts have trace elements like S, Ca, Br and Sr in different proportions. The pink salt appears to be
characterized by relatively large amounts of Mg, Si, K, Ti and Fe. The differences observed are discussed in terms of origin of the product.

1. Introduction countries. For instance, the salt consumption of the United States
topped about 53 billion kilograms in 2008 [3]. At that time, ice control
Chlorine is one of the seven micronutrients essential for plants. and chemical industry were the main end-users of salt in this country
Together with sodium, it figures among those elements essential to [3].
living organisms including humans. In this way, sodium chloride (NaCl) Despite its relatively small salt production, Pakistan came into the
present in salt becomes an important daily source of these elements. international scenario thanks to what has been known as Himalayan
Sodium chlorine has a 1:1 stoichiometry and it is made up by 23Na salt. Himalayan salt comes from Khewra, Kalabagh and other mines
(22.99 amu) and by 35Cl (34.97 amu) and 37Cl (36.97 amu) isotopes. located in Salt Range Hills about 300 km southwest of the Himalayas.
Therefore, 100 g of sodium chloride has 39.34 g of Na and 60.66 g of Cl. Himalayan salt is also known as pink salt and it is becoming more and
Salt is usually white but inclusions of other minerals at the trace level (a more popular not only in haute cuisine but also in several homes due to
few parts per million) may change its color. In principle, salt should be its allegedly properties including richness in mineral content. Besides
free of organic compounds. However, it has been shown that some Na and Cl, other trace elements like Cr, Fe and Zn among others were
synthetic organic compounds may be found in salt due to transportation found in Khewra salts [1,4–6]. According to a comparative sensorial
and storage of rock salt [1]. study of salts from several countries [5], Himalayan salt has larger
Salt is considered a commodity and is usually used as seasoning and concentrations of Ca, K, Mg and Fe than Brazilian salts. According to
food preservative and can be found in different granule sizes, varying the same study, the impact of trace elements on flavor is small. How-
from a relatively fine powder to small crystals. The most common salt is ever, distinct flavors are noticeable when sea salts are compared with
table salt which is usually refined through different processes. Usually, table salt. Moreover, some trace elements are correlated with different
these processes include the addition of potassium iodide (KI) together sensations like astringency and bitterness [5].
with some anticaking agents like sodium aluminusilicate (NaAlSi3O8) The Himalayan salt sold in the Brazilian market is imported and
and magnesium carbonate (MgCO3). The main sources of salt are sea- consequently more expensive than marine salt produced locally. Since
water, brine from wells and rock salt from mines. food fraud is rampant worldwide, a question arises whether it would be
According to the British Geological Survey, the global production of possible to counterfeit this salt by any kind of manipulation. In this way,
salt reached about 280 billion kilograms in 2016 [2]. China, United we embarked on the assessment of the elemental profile of several
States and India are responsible for about half of the global production Brazilian salts in order to compare them with Himalayan salts. To that
while Brazil and Pakistan contribute to only 2.7% and 1.4% respec- end, the PIXE (Particle-Induced X-ray Emission) technique [7] was em-
tively [2]. This production is used in different ways according to ployed in order to obtain the concentrations of major and trace elements.


Corresponding author at: Ion Implantation Laboratory, Institute of Physics, UFRGS, Brazil.
E-mail address: jfdias@if.ufrgs.br (J.F. Dias).

https://doi.org/10.1016/j.nimb.2019.07.008
Received 17 April 2019; Received in revised form 4 July 2019; Accepted 5 July 2019
Available online 09 July 2019
0168-583X/ © 2019 Elsevier B.V. All rights reserved.
T. Kuhn, et al. Nuclear Inst. and Methods in Physics Research B 477 (2020) 150–153

Fig. 1. X-ray spectra as a function of the X-ray energy obtained from four dif- Fig. 2. X-ray spectra as a function of the X-ray energy between 0 and 6 keV
ferent brands of marine Brazilian salts. Brand 1 provides both refined and obtained from Himalayan salts. White and red crystals were selected from raw
crystal salts. All spectra represents an average of several independent spectra Himalyan salts. All spectra represents an average of several independent spectra
and are normalized by the charge accumulated during the experiments. and are normalized by the charge accumulated during the experiments.

2. Materials and methods

2.1. Samples

In order to evaluate the variance of the elemental concentrations


found in Brazilian salts, four brands of Brazilian marine salts and three
brands of Himalayan salts were purchased in the local market. One of
the Brazilian brands was sold as refined table salt and crystal salt. Seven
samples of each brand were analyzed, totaling 56 samples. Finally, two
samples of each Himalayan brand was prepared for comparison pur-
poses: one with the white crystals; and another one with red crystals. In
this case, the crystals were sorted out by hand according to their color.
For the PIXE experiments, the samples were crushed, homogenized
and pressed into 2 mm thick pellets of 25 mm diameter. In order to
avoid contamination by Fe from the piston used for the pressing of the
salt, a disk of polymer was used to separate the piston from the salt.

2.2. PIXE experiments Fig. 3. X-ray spectra as a function of the X-ray energy between 6 and 17 keV
obtained from Himalayan salts. White and red crystals were selected from raw
A 3 MV Tandetron accelerator provided 2.0 MeV H+ ions with re- Himalyan salts. All spectra represents an average of several independent spectra
latively low currents (about 0.4 nA) in order to keep the experimental and are normalized by the charge accumulated during the experiments.
dead time at acceptable levels. The beam spot size was 4 mm2 at the
samples. The reaction chamber was kept under a pressure of about

Table 1
Elemental concentrations of Brazilian salts. All results are represented by the mean and the respective standard deviation of the mean. All values are given in parts per
million (ppm). Some results were compatible with the limit of detection (LOD). The recommended values shown in the last column were calculated based on the
recommended intake per day of sodium chloride (1), on the recommended dietary allowance (2) and on the adequate intake (3) values extracted from reference [13].
It was assumed that the adequate intake of sodium chloride is 3.8 g per day.
Element Brand 1 (Refined) (ppm) Brand 4 (ppm) Other Brands (ppm) Recommended (ppm/day)

Na 389142 ± 27524 384596 ± 27035 380687 ± 26744 3934001


Mg 763 ± 147 214 ± 95 599 ± 175 934212
Al 90 ± 41 162 ± 58 111 ± 26 –
Si 834 ± 131 125 ± 38 140 ± 84 –
S 454 ± 96 2320 ± 439 1071 ± 219 –
Cl 608489 ± 31165 602932 ± 30550 601557 ± 30180 6066001
K 368 ± 56 723 ± 153 251 ± 42 12368423
Ca 72 ± 30 (LOD) 1122 ± 327 2054 ± 215 2631583
Ti 8 ± 3 (LOD) 12 ± 4 (LOD) 6 ± 2 (LOD) –
Mn 5 ± 1 (LOD) 5 ± 1 (LOD) 4 ± 1 (LOD) 5393
Fe 8 ± 5 (LOD) 13 ± 3 3 ± 1 (LOD) 34212
Br 177 ± 11 5±2 150 ± 6 –
Sr 1 ± 1 (LOD) 14 ± 5 40 ± 7 –

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T. Kuhn, et al. Nuclear Inst. and Methods in Physics Research B 477 (2020) 150–153

Table 2
Elemental concentrations of Himalayan salts. All results are represented by the mean and the respective standard deviation of the mean. All values are given in parts
per million (ppm). Some results were compatible with the limit of detection (LOD). Red and white crystals were selected from raw Himalayan salts. The re-
commended values shown in the last column were calculated based on the recommended intake per day of sodium chloride (1), on the recommended dietary
allowance (2) and on the adequate intake (3) values extracted from reference [13]. It was assumed that the adequate intake of sodium chloride is 3.8 g per day.
Element Himalayan (ppm) Himalayan Red Crystals (ppm) Himalayan White Crystals (ppm) Recommended (ppm)

Na 366714 ± 25786 315086 ± 22529 382220 ± 27163 3934001


Mg 4500 ± 488 13276 ± 933 824 ± 285 934212
Al 686 ± 114 1909 ± 196 146 ± 44 –
Si 2141 ± 277 8201 ± 618 248 ± 103 –
S 6703 ± 608 16260 ± 1186 1606 ± 296 –
Cl 581430 ± 29318 516290 ± 26653 597645 ± 30490 6066001
K 6320 ± 1200 19307 ± 2647 915 ± 158 12368423
Ca 2970 ± 242 14849 ± 2023 781 ± 206 2631583
Ti 35 ± 8 146 ± 28 6 ± 2 (LOD) –
Mn 7±1 26 ± 6 3 ± 2 (LOD) 5393
Fe 244 ± 28 880 ± 185 15 ± 1 34212
Br 61 ± 2 56 ± 2 58 ± 3 –
Sr 28 ± 3 137 ± 22 9±3 –

elemental concentrations. The standardization procedure was carried


out with high purity NaCl, KCl and thin X-ray standards.
Finally, the final results are represented by the mean and the re-
spective standard deviation.

3. Results and discussion

Fig. 1 shows the normalized X-ray spectra of all Brazilian salts


measured in this work. The spectra are dominated by Na and Cl. Traces
of Mg, Al, K, Br and Sr are observed in some brands. Concerning Fe,
only brand 4 had concentrations above the limit of detection (LOD).
Table 1 shows the results of Brand 1 (refined salt), Brand 4 and the
average of all other brands. The results obtained in this work for Mg are
systematically higher than those reported in reference [5]. On the other
hand, the concentrations of Fe reported in Ref. [5] (2.6 ppm) agrees
with the results obtained in this work for Brand 1 (refined) and all other
Fig. 4. X-ray spectra as a function of the X-ray energy obtained from all Brazilian brands and is smaller than the results obtained for Brand 4.
Brazilian salts and from white crystals selected from raw Himalayan salts. All While the concentrations of Ca obtained in this work for Brand 4 and all
spectra represents an average of several independent spectra and are normal- other brands are higher than those reported in reference [5] (700 ppm),
ized by the charge accumulated during the experiments. the opposite is true as far as K is concerned (2200 ppm). With respect to
the refined salt measured in this work, the elemental concentrations of
10−6 mbar. The charge accumulated during the experiments were in- S, Ca and Sr are smaller than those found in crystal salts (represented by
tegrated in the PIXE chamber itself since it is completely insulated from the average of other brands in Table 1) while Si is much higher. One
the accelerator and other devices. The charge accumulated during each possible explanation for the large concentration of Si found in the re-
irradiation was about 0.7 μC. Finally, an electron flood gun was used in fined salt is the addition of silicates in the salt processing in order to act
all experiments in order to avoid charge buildup in the samples [8]. as an anticaking agent.
The detection system consisted of a Si(Li) detector placed at −135° Figs. 2 and 3 present the normalized averaged spectra of the Hi-
with respect to the proton beam. The energy resolution of the detector malayan salts in two distinct energy regions: i) from 0 to 6 keV (Fig. 2);
is about 150 eV at 5.9 keV. The detector’s efficiency curve was obtained ii) and from 6 to 17 keV (Fig. 3). The results obtained for red and white
elsewhere [9]. The crystal thickness is 4.5 mm. This relatively thin crystals of the Himalayan salts are shown as well. Clearly, the con-
crystal together with 2 MeV protons reduce the influence of the centration of several minerals is much higher in red crystals than the
Compton scattering background due to the excitation of the 440 keV concentrations found in white crystals. These results are summarized in
gamma line of 23Na. Finally, the detector window consisted of a 12 μm Table 2. The elemental concentrations obtained in this work for Mg, K,
thick Be. Neither absorbers nor magnets were employed in the experi- Ca and Fe are systematically higher than those reported in reference [5]
ments. (1060 ppm, 2800 ppm, 1600 ppm and 36.9 ppm respectively). On the
other hand, our results for Fe are much smaller than those found in
reference [4] (2400 ppm).
2.3. Data analysis Our results show that the Fe concentration of the Himalayan red
crystals is about 60 times higher than the concentration found in
The PIXE spectra were analyzed with the GUPIXWIN software de- Himalayan white crystals. Indeed, the presence of Fe in colored salts is
veloped at the University of Guelph [10,11]. All important experi- much higher than in white salts [12]. Interestingly, the analysis of red
mental parameters and physical effects like secondary fluorescence and salt from Khewra carried out by Sharif and collaborators [4] suggests a
X-ray self-absorption in the target are computed by this software. concentration of 4600 ppm, which is about the same concentration
Moreover, it makes use of a comprehensive database including stopping found by the same author in white crystal salt from the same place
and ionization cross sections among others. Through the so-called H (4800 ppm). Finally, our results for the contents of Sr in Himalayan salt
value standardization procedure [7], peak areas are converted into is smaller than the concentration found by Rahman and co-workers in

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T. Kuhn, et al. Nuclear Inst. and Methods in Physics Research B 477 (2020) 150–153

salts from Khewra [6] (45 ppm). straightforward and does not require any kind of treatment prior to the
Fig. 4 shows the X-ray spectra of Himalayan white crystals together measurements.
with an average spectrum of all Brazilian salts studied in this work. The
Brazilian salts include white crystal salts and refined salts. The con- Acknowledgments
centration of Sr in Brazilian salts is higher than that found in white
crystals from Himalayan salts. Apart from that, both spectra looks quite The authors acknowledge the partial financial support from the
similar, indicating white salts are characterized by the much smaller Brazilian agencies CAPES and CNPq. Moreover, this project is part of
concentrations of trace elements like Mg and Fe. the Coordinated Research Project F11021 sponsored by the
International Atomic Energy Agency (IAEA) under contract number
4. Conclusions 21125.

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