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Article

Assessment of Heavy Metals and Radionuclides Concentration in Selected Mineral Waters Available on the Polish Market

by
Małgorzata Wojtkowska
1,*,
Karol Wojtkowski
2 and
Magdalena Długosz-Lisiecka
3
1
Faculty of Building Services, Hydro and Environmental Engineering, Warsaw University of Technology, Nowomiejska 20, 00-653 Warszawa, Poland
2
Central Laboratory for Radiological Protection, 7 Konwaliowa Street, 03-194 Warsaw, Poland
3
Institute of Applied Radiation Chemistry, Lodz University of Technology, Wróblewskiego 15, 90-924 Łódź, Poland
*
Author to whom correspondence should be addressed.
Appl. Sci. 2022, 12(22), 11401; https://doi.org/10.3390/app122211401
Submission received: 11 October 2022 / Revised: 4 November 2022 / Accepted: 7 November 2022 / Published: 10 November 2022
(This article belongs to the Special Issue Water and Wastewater Management in Agriculture)
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Abstract

:
This research examined samples of mineral water available on the Polish market. The contents of radionuclides in 12 samples of water were determined: cesium 137Cs, thorium 232Th, potassium 40K, and radium 226Ra; and heavy metals: zinc, copper, chromium, nickel, lead, cadmium, and mercury. Spectrometric analysis showed the presence of a 232Th track in one sample (Franciszek water) with a concentration of 2.4 ± 2.1 mBq/L above the LLD (low limit of detection); 40K potassium was detected in all samples. In the case of radium 226Ra, its presence above the detection threshold was found in nine water samples. No artificial element 137Cs was found in the mineral waters. The tests showed the concentrations of heavy metals (Cd, Cr, Cu, Hg, Ni, and Pb) present in the waters. The limit values are specified by the Ministry of Health Regulation. Copper, cadmium, and chromium did not exceed the permissible values. In the case of nickel, the normalized values (20 μg/L) were exceeded in only two waters: Słotwinka and Józefowianka. Only in the Amita water did we find that the value of 1.0 μg/L was exceeded. The concentration of zinc, for which no limit is set in the regulation, was the highest, ranging from 287 to 1.30 μg/L. The greatest threat to people drinking the studied mineral waters is lead, which in eight waters exceeded the permissible value of 10 μg/L.

1. Introduction

Worldwide, the availability of freshwater is declining, especially in developing countries. The reasons are pollution and water scarcity [1]. Rapid industrialization and urbanization with poor wastewater and pollution management have become a big problem [1,2,3]. In water systems, metal pollution that is difficult to isolate can pose a threat to human health and the aquatic ecosystem [4,5]. Contaminated waters are often recycled in physicochemical and biological processes. Humans drink water daily, and recently there has been an increase in the consumption of bottled natural mineral and spring water. Owing to the depth of extraction, the waters available on the domestic market can be divided into two categories. The first category is water from surface sources or shallow wells, up to 20 m. The second category consists of highly mineralized healing waters, which are extracted from deep wells [6]. Taking into account the location and depth of water, the water may contain trace metals, natural metals, and artificial radionuclides.
The observed environmental pollution caused by heavy metals is a reflection of air, water, and soil contamination by dust, industrial gases, sewage, waste, and coal combustion processes. The concentrations of heavy metals in the environment are quite diverse, and their effect depends on the dose, the type of element, the chemical form in which it occurs, and even the condition of the organism [7]. The phenomenon of increased concentrations of trace elements is especially visible for inland surface waters, as well as coastal marine waters, soil waters, and shallow groundwater. Water pollution is of particular importance due to the role of water in the circulation of elements in various environments.
The concentration of heavy metals in water depends mainly on their chemical properties, including forms of occurrence and solubility [8]. The mobility of these pollutants in water depends on the parameters of the aquatic environment. These include, first of all, the pH, the redox potential, and the ability to form soluble complexes. Water is fit for use if it is free from any substances in concentrations that may pose a risk to human health. In accordance with the Health Minister (2017) ordinance that regulates the requirements for the content of heavy metals in drinking water, metal concentrations should not exceed the following values: cadmium < 5.0 μg/L, copper < 2.0 mg/L, mercury < 1.0 μg/L, nickel < 20 μg/L, and lead < 10 μg/L [9].
Trace metals present in water exist in the form of soluble and insoluble chemical compounds. They bind to solid or colloidal particles and accumulate in sediments and tissues of organisms. Bound metals in the body can reveal toxic properties if they are in an absorbable form at a concentration that causes an adverse reaction by the body. The toxic potential of trace metals to organisms depends on many factors. These are the composition and health of the organisms together with the form, properties, concentration, and availability of the trace metal.
Certain trace metals play the role of micronutrients, serving an important role in keeping organisms alive. Trace metals are essential for metabolism. They are supplied mainly with food and water. Elements such as iron and zinc play an important role in the development and functioning of the human body. Additionally, for proper functioning of the body, much smaller amounts of chromium, cobalt, manganese, molybdenum, nickel, selenium, and vanadium are needed [10]. In the body, they perform their function only in certain concentrations. The toxic properties are manifested only when the concentration available to the body exceeds the value necessary to meet the nutritional needs. Toxic concentrations of, e.g., zinc compounds toward plants, aquatic microorganisms, and fish are very low; their toxic value have been determined to be above 0.1 mg/L.
Some trace metals play no role in the life cycle of organisms and belong to the group of toxic compounds. By accumulating in the body, they cause many diseases and create a risk for abnormal development [11]. These include As, Cd, Hg, and Pb, which can cause damage to the organism if they are available in the environment in a concentration exceeding the permissible concentration.
The chemical composition of drinking water depends on the composition of the substrate and the topography. Currently, it is common to consume mineral waters. Poland is a country rich in mineral water sources that can be exploited. Sources in Poland are among the largest in the world [12]. Water from each source has its own composition and can be used for different purposes. The composition of mineral waters depends on the geological structure of the areas around the deposit. The basic ions found in water are anions: bicarbonate (HCO3−), chloride (Cl−), and sulfate (SO42−), and cations: calcium (Ca2+) and magnesium (Mg2+). The condition for classifying water to a specific group of mineral waters is the content of a given ion above 20% of milligram equivalents, assuming that the sum of cations and anions is 100% [13].
Ionizing radiation is an inseparable companion of human life. Every day we are exposed to radiation that comes from various sources. Contamination of drinking water can cause various safety complications for human health [14]. Human activity is a more important factor influencing the physicochemical properties of water quality and is growing rapidly in developing countries around the world [15]. The consumption of water containing significant amounts of metals can cause serious health effects in humans. Copper (Cu) in drinking water in large amounts can cause stomach upset, nausea, diarrhea, and liver damage [16]. Exposure to nickel (Ni) by dermal and oral routes may cause allergies, pulmonary fibrosis, cardiovascular and renal diseases, and respiratory-tract cancer [17,18]. Cadmium over-absorption can cause kidney damage, respiratory distress, and bone damage [19,20,21]. Cadmium is also a carcinogenic metal with a 38-year half-life, which causes Cd to be retained in the body [22]. Humans are also naturally exposed to ionizing radiation from several sources, e.g., cosmic rays and natural radionuclides in air, food, and drinking water [23,24]. Radiation is one of the natural phenomena in the environment [25].
Exposure to ionizing radiation from artificial radionuclides is related, among others, to medicine (radiotherapy, curieterotherapy) and industry (nuclear power plants) [26]. The presence of anthropogenic radionuclides in the environment is also related to human activity, e.g., failure of nuclear power plants (Fukushima, Chernobyl) or tests of nuclear weapons carried out in large numbers in the 1950s and 1960s [27,28]. Natural radionuclides occurring in the environment are of cosmogenic origin or were formed during the formation of the Earth. The latter penetrate into various components of the environment, including into water as a result of erosion and weathering of rocks. The concentration of radionuclides in a given area depends on the geological characteristics of that area. Water can be a source of radiation because it contains some naturally occurring radionuclides [29]. Radionuclides are characterized by long half-lives comparable to the time of the Earth’s existence [30]. This group also includes radionuclides derived from long-lived parent elements of three natural radioactive series: uranium–radium, uranium–actinium, and thorium [31].
The presence of radionuclides in drinking water causes many potential health risks, especially when these radionuclides accumulate in the human body [23,24]. In order to control radionuclides, it is necessary to evaluate the effective dose in order to predict possible biological damage to the organism. In developing countries, about 80% of the world’s diseases and over a third of deaths occur due to water pollution [32]. Radionuclides show special features due to their very long half-life. For the correct assessment of human exposure, it is necessary to assess water quality, including the content of heavy metals and the presence of radionuclides [33]. Long-lived isotopes that can pose a threat to human health and life are particularly important. They also have an impact on the effective dose that a person receives as a result of their consumption with water [34,35]. Each country has legal regulations regarding radiological requirements that water should meet. In Poland, this is included in the Regulation of the Minister of Health of 7 December 2017 [9] on the quality of water intended for human consumption. The requirements stipulate that the permissible concentration of tritium in drinking water must not exceed 100 Bq/L, and the total permissible dose is 0.1 mSv/a [8]. It should be mentioned that if the total α radioactivity is not higher than 0.1 Bq/L and the total β radioactivity is not higher than 1 Bq/L, the dose limit is not exceeded [36,37].
In the United States, the applicable legal regulations stipulate that the total concentration of 228Ra and 226Ra should be measured, and the total level of contamination must not exceed 185 MBq/L [38]. In Turkey and Hungary, according to the regulations in force, there are limit values for alpha and beta radiation, respectively: 0.1 Bq/L and 1 Bq/L [39,40]. In Australia, the total effective dose of radionuclides (without 40K potassium) in drinking water should not be greater than 1 mSv/a [41,42]. Artificial radionuclides are found mainly in surface waters. Their occurrence is related to the operation of nuclear facilities including nuclear power plants, the processing of spent nuclear fuel, and the production of radiopharmaceuticals. Drinking water is drawn from deep underground aquifers that are not exposed to contamination from anthropogenic radioactive elements. Natural radionuclides, found in the Earth’s crust and thus also in deep-sea drinking waters, can be present in high concentrations and make a significant contribution to the total dose for consumers [43,44]. In particular, long-life elements 40K, 210Pb, 226Ra, 232Th, and 238U are important. For example, radioactive radon 226Ra decays into alpha radioactive radon 222Rn. It causes exposure of the lung epithelium to neoplastic changes [45,46]. Knowledge of the distribution pathways for both metals and radionuclides is essential to maintain control of prevailing levels of contamination, radiation, and radioactive contamination. The aim of this study was to evaluate the contamination of mineral waters due to the content of trace metals and natural (40K—energy 1460 keV, 226Ra—186 keV, 232Th—63.8 keV) and artificial (137Cs—662 keV) levels of radioactivity in water samples available on the Polish market.

2. Materials and Methods

This article presents the results of measurements on 12 types of mineral waters available in the domestic market. The tests included measurements of the presence of radionuclides and the content of heavy metals. The samples were initially acidified with concentrated HNO3 (60% concentration) to stabilize the water components. The water for radionuclide measurements was concentrated by evaporation at 90 °C to a volume of 0.5 l. The cooled water was placed in a Marinelli Biker container. Following the recommendation from the International Atomic Energy Agency in Vienna, the samples were measured using spectrometric analysis of gamma radiation in the photon energy range from 50 to 1800 keV. The measurement time for each sample was 80,000 s. For the measurement of radionuclide concentrations in the water samples, Canberra gamma radiation spectrometers with 40% and 30% HPGe semiconductor detectors were used, operating in conjunction with a Model DSA-2000 analyzer and equipped with GENIE-2000 software, which enabled identification of radionuclides and their quantitative analysis. The total uncertainty in determining the concentration of individual radionuclides did not exceed ± 20%. For the calibration of the spectrometers, reference sources were used in the geometry of the Marinelli vessel with a volume of 0.5 L (with two different dimensions of the cavity), density 1.3 g/cm3, containing a mixture of the following radioactive radionuclides: 109Cd, 57Co, 60Co, 139Ce, 137Cs, 203Hg, 85Sr, 113Sn, and 88Y. The uncertainty of determining individual radionuclides in the standards did not exceed 5%. To reduce the size of the external radiation background, the detector was placed in a shielding house with walls composed of three layers: 100 mm thick outer and Pb lead, another 1 mm Cd cadmium sheet, and 2 mm Cu copper inner sheet. Radioactive elements can migrate to human body through inhalation or by eating meals or water [47,48]. The need to monitor the quality of mineral waters results from the increase in human water consumption in recent years. In Poland, the Regulation of the Minister of Health of 31 March 2011 on natural mineral waters, spring waters, and table waters is in force. The aspects related to the presence of radioactive elements in the abovementioned waters are included in the Regulation of the Minister of Health of 11 December 2017 [49]. The regulation contains radiological requirements to be met by water. The total allowable dose is 0.1 mSv/a. The limit dose may be exceeded when the total α radioactivity exceeds 0.1 Bq/L and the total β radioactivity exceeds 1 Bq/L [9]. Moreover, it should be emphasized that the concept of a parametric value was formulated in the Euroatom Council Directive 2013/51 [50]. It is “the content of radioactive substances in water, above which it is necessary to assess whether the presence of radioactive substances in water poses a risk to human health, and, if necessary, to take appropriate corrective measures to improve the water quality to a level consistent with the requirements of protecting human health against radiation” [51].
The measurement results obtained in the further part of this study were used to assess the exposure to ionizing radiation in the event of absorption of radionuclides with consumed mineral water during the year for individual age groups. In order to estimate the annual effective dose, the values of the transition coefficients included in the Regulation of the Council of Ministers of 18 January 2005 on the limit doses of ionizing radiation, Journal of Laws No. 20, item 168. When estimating the annual effective dose, the following formula was used [52]:
Ed = Σdci · Ci · V
where:
Ed—effective dose (mSv/a);
dci—dose coefficient for given nuclide (mSv/Bq);
Ci—given radionuclide concentration (Bq/L);
V—annual water consumption (L).
This article presents the results of tests for zinc, copper, chromium, nickel, lead, cadmium, and mercury in 12 samples of mineral water. Qualitative analysis was performed using the spectrometric atomic absorption method with atomization in a graphite furnace. The analysis of the collected water samples was carried out in accordance with the applicable standards for water sampling [52] and their quantification [53]. The procedure for determining the concentration of trace elements in mineral water was performed without preliminary sample preparation. For this purpose, samples of water were taken into properly prepared vessels, and then, to ensure their stability, 0.3 mL of concentrated nitric acid was added and analyzed within a short time.

3. Results and Discussion

3.1. Analysis of Research on the Presence of Radioactive Elements

This study analyzed 12 water samples, which were characterized by high content of minerals. The water was purchased in supermarkets in Warsaw. They come from deep water intakes located in Poland and were also bottled. Spectrometric analysis did not show the presence of the artificial element 137Cs above the LLD (low limit of detection) measurability. In one of the tested samples, the presence of a 232Th track above the measurability threshold (Franciszek water) was found. Its concentration was 2.4 ± 2.1 mBq/L. In all samples, 40K potassium above the measurable limit was detected. In the case of radium 226Ra, its presence above the detection threshold was found in nine water samples. Table 1 shows the concentration of 40K potassium and 226Ra radium activity for the tested mineral water samples, together with the minimum and maximum values, the median, the coefficient of variation, the mean, and the standard deviation. Figure 1 shows the concentration of 40K potassium activity in the samples of mineral waters. The orange line represents the mean value for the set of samples.
The lowest concentration of 40K potassium was found in the Nałęczowianka water sample, 151.40 ± 15.40 mBq/L. The maximum value was measured for the Franciszek water sample, 468.7 ± 32.10 mBq/L. It is more than three times the minimum value. For all samples, the mean concentration of 40K potassium was 356.63 ± 26.08 mBq/L (Figure 1).
Figure 2 shows the concentration of radium 226Ra activity in nine samples of mineral waters. The red line represents the mean value for the set of samples. The lowest concentration (below the detection level) of radium 226Ra was found in three water samples: Józefowianka, Słotwinka, and Zuber. The maximum value occurred for the Amita water sample, 32.6 ± 9.4 mBq/L. For all samples where the concentration was above the LLD, the average concentration of radium 226Ra was 14.8 ± 7.8 mBq/L. Above average activity concentrations were recorded in three samples.
The values of the annual consumption of mineral water by different age groups, the values of the transition coefficients, and the annual effective doses for individual radionuclides are given in Table 2, Table 3 and Table 4.
Based on the obtained values, total annual effective doses were determined. In the case of children up to 1 year of age, the dose values ranged from 5.85 ± 0.42 to 43.71 ± 12.90 μSv/a. The mean value for all waters was 18.84 ± 7.46 μSv/a. The values of annual effective doses for children under 1 year of age from the consumption of individual mineral waters are presented on Figure 3. The average value is marked with a purple line.
Annual effective doses for children aged 1 to 10 ranged from 3.70 ± 0.27 to 12.43 ± 2.94 μSv/a. The mean value for all waters was 6.60 ± 1.89 μSv/a. The annual effective doses for children from 1 to 10 years of age after consumption of individual mineral waters are presented in Figure 4. The mean value is marked with the brown line.
Annual effective doses for adolescents aged 10 to 17 ranged from 1.55 ± 0.11 to 27.84 ± 7.72 μSv/a. The mean value for all waters was 10.51 ± 4.86 μSv/a. The values of annual effective doses for adolescents aged 10 to 17 years after the consumption of individual mineral waters are presented in Figure 5. The average value is marked with the navy blue line.
Annual effective doses for adults ranged from 1.71 ± 0.12 to 8.24 ± 2.24 μSv/a. The mean value for all waters was 3.92 ± 1.34 μSv/a. Annual effective doses for adults from consumption of particular mineral waters are shown in Figure 6. The average value is marked with the red line.
Adults were selected as the comparison group. Table 5 shows the average values of annual effective doses for mineral waters consumed in Poland and other countries.
From the values presented, Table 5 shows that the dose of water consumption received by an adult resident of Poland is over 70 times lower than the global values. The value of the annual effective dose from the consumption of mineral water available on the domestic market is similar to bottled waters in Turkey, Portugal, or Japan. The low value of the annual effective dose is related to the fact that the waters, e.g., in Iran, contain large amounts of radium 226Ra, which when decaying emit alpha-radioactive radon 222Rn [59].

3.2. Analysis of Heavy Metals

Tests for trace metals were carried out on 12 samples of mineral water collected in August 2018. The obtained results showed very different concentrations in the analyzed mineral waters. Table 6 presents the results of the metal composition tests carried out on the natural bottled water samples selected for the tests.
The obtained results are shown in Figure 7, Figure 8, Figure 9, Figure 10, Figure 11, Figure 12 and Figure 13. The performed tests showed that in the mineral water samples selected for analysis, zinc concentrations ranged from 287.5 μg/L in Amita water to 1300 μg/L in Nałęczowianka water. It should be noted that requirements for drinking water are not specified for zinc. Trace metals, defined as micronutrients and standardized in the MH Regulation of 2017, are copper, nickel, chromium, lead, cadmium, and mercury. The highest concentration of copper was in Słotwinka water, 400 μg/L, and the lowest, 31.3 μg/L, in Żywiecki-Kryształ water. It should be noted that in all mineral waters the value of 2 μg/L Cu, specified in the ordinance of the Minister of Health of 2017, was exceeded. Nickel concentrations ranged from 3.6 μg/L in Laguna water to 37 μg/L in Słotwinka water. In the case of nickel, the normalized values (20 μg/L) were exceeded in only two waters: Słotwinka and Józefowianka (31.8 μg/L). The concentration of chromium and cadmium in all waters was below the acceptable value of 50 and 5 μg/L, respectively. For Cr and Cd, the lowest and the highest concentrations were found for the same mineral waters: Józefowianka, 0.7 and 3.4 μg/L, respectively, and Słotwinka, 2.8 and 46.8 μg/L, respectively. Mercury concentration in 11 waters was below the standard value (1.0 µg/L). Only in the Amita water did we find an exceedance, 1.4 μg/L. The greatest exceedances of the permissible value (10.0 μg/L) were recorded for lead. The concentration range for Pb was 5.2–41.8 μg/L. The highest concentrations were found in the following waters: Zuber—41.8 μg/L, Józefowianka—37.0 μg/L, and Słotwinka—39.8 μg/L. The best water for its low lead content was Franciszek.
The performed tests showed that in the mineral water samples selected for analysis, zinc was present in the range from 287.5 μg/L in Amita water to 1300 μg/L in Nałęczowianka water. It should be noted that for drinking water, zinc does not have a specific limit value required. Trace metals, defined as micronutrients and standardized in the MH regulation of 2017, are copper, nickel, chromium, lead, cadmium, and mercury. The highest concentration of copper was in Słotwinka water, 400 μg/L, and the lowest, 31.3 μg/L, in Żywiecki-Kryształ water. It should be noted that in all mineral waters, the value 2 μg/L Cu, specified in the ordinance of the Minister of Health of 2017, was exceeded. Nickel concentrations ranged from 3.6 μg/L in Laguna water to 37 μg/L in Słotwinka water. In the case of nickel, the normalized values (20 μg/L) were exceeded in only two waters: Słotwinka and Józefowianka (31.8 μg/L). The concentration of chromium and cadmium in all waters was below the acceptable values of 50 and 5 μg/L, respectively. For Cr and Cd, the lowest and the highest concentrations were found for the same mineral waters: Józefowianka 0.7 and 3.4 μg/L, respectively, and Słotwinka 2.8 and 46.8 μg/L, respectively. The mercury concentration in 11 waters was below the standard value (1.0 µg/L). Only in the Amita water did we found an exceedance, 1.4 μg/L. The greatest exceedances of the permissible value (10.0 μg/L) were recorded for lead. The concentration range for Pb was 5.2–41.8 μg/L. The highest concentrations were found in the following waters: Zuber—41.8 μg/L, Józefowianka—37.0 μg/L, and Słotwinka—39.8 μg/L. The best water for its low lead content is Franciszek.

4. Conclusions

Taking into account the requirements included in the regulation of the Minister of Health of 11 December 2017 [9] and comparing them with the results of measurements of the tested water samples, it was found that the concentration values of the activity of radioactive elements did not exceed the permissible limits specified in the regulation. The obtained results were compared with those obtained in other regions of the world.
Trace amounts of radium 226Ra were detected in the investigated waters. The differences in the amount of radium 226Ra in the waters are due to the soil structure and its composition [60,61,62]. The nature of the tested water is also an important aspect. Deep water and spring waters are rich in natural radioactive elements—this enrichment results from their leaching from the soil structure. On the other hand, groundwater has a much larger number of elements from an artificial origin, such as strontium 90Sr or cesium 137Cs. When analyzing the effective doses for the tested mineral waters from Poland, the highest value was determined in the Amita water sample. It should be emphasized that the determined effective dose, e.g., for an adult, does not pose a threat to human health and life; it constitutes about 0.8% of the limit and permissible value, which is 1 mSv/a, in accordance with the applicable “Atomic Law”, and 8% of the limit value for drinking water, which is 0.1 mSv/a. It follows that consumption of mineral waters available on the domestic market does not pose a threat to human health and life from the point of view of radiological protection.
The investigated mineral waters were rich in trace elements. As a result of the analysis, it was found that the waters were most rich in zinc and copper, micronutrients necessary for proper human development. The most dangerous metals, cadmium and mercury, in all waters were below the limit values specified in the Ministry of Health Regulation of 2017 [9]. In the investigated mineral waters, chromium and nickel are not a problem. The greatest threat to people drinking the investigated mineral waters is lead, which in eight waters exceeded the permissible value. Among the analyzed waters, the best quality in terms of the concentration of all metals was demonstrated by the waters of Żywiecki-Kryształ, Primavera, Henryk, and Franciszek.
Drinking water should be subject to constant control and protection against possible contamination. If the water does not meet the basic criteria that qualify it for household use, it cannot be consumed by humans. Heavy metals tend to accumulate in organisms. After a while, regularly taking small doses begins to manifest itself with various health problems, depending on the properties of the metal.

Author Contributions

For all author contributions, it is conceptualization 33%, methodology 33%, research 33%, formal analysis 33%, writing—review and editing 33%and article preparation, project administration, 33%.; funding acquisition, 33%. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Informed consent was obtained from all subjects involved in the study.

Data Availability Statement

Not applicable.

Conflicts of Interest

The authors declare no conflict of interest.

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Applsci 12 11401 g001 550
Figure 1. Concentration of 40K potassium activity in the samples of mineral waters. The orange line represents the mean value for the set of samples.
Figure 1. Concentration of 40K potassium activity in the samples of mineral waters. The orange line represents the mean value for the set of samples.
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Figure 2. Concentrations of radium 226Ra activity in 9 samples of mineral waters. The red line represents the mean value for the set of samples.
Figure 2. Concentrations of radium 226Ra activity in 9 samples of mineral waters. The red line represents the mean value for the set of samples.
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Figure 3. Annual effective dose for children under 1 year of age from the consumption of individual mineral waters.
Figure 3. Annual effective dose for children under 1 year of age from the consumption of individual mineral waters.
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Figure 4. Annual effective dose for children from 1 to 10 years of age from the consumption of individual mineral waters.
Figure 4. Annual effective dose for children from 1 to 10 years of age from the consumption of individual mineral waters.
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Figure 5. Annual effective dose for adolescents from 10 to 17 years of age from the consumption of individual mineral waters.
Figure 5. Annual effective dose for adolescents from 10 to 17 years of age from the consumption of individual mineral waters.
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Figure 6. Annual effective dose for adults from the consumption of individual mineral waters.
Figure 6. Annual effective dose for adults from the consumption of individual mineral waters.
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Figure 7. The concentration of lead in mineral waters (μg/L).
Figure 7. The concentration of lead in mineral waters (μg/L).
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Figure 8. The concentration of cadmium in mineral waters (μg/L).
Figure 8. The concentration of cadmium in mineral waters (μg/L).
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Figure 9. The concentration of chromium in mineral waters (μg/L).
Figure 9. The concentration of chromium in mineral waters (μg/L).
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Figure 10. The concentration of copper in mineral waters (μg/L).
Figure 10. The concentration of copper in mineral waters (μg/L).
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Figure 11. The concentration of nickel in mineral waters (μg/L).
Figure 11. The concentration of nickel in mineral waters (μg/L).
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Figure 12. The concentration of mercury in mineral waters (μg/L).
Figure 12. The concentration of mercury in mineral waters (μg/L).
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Figure 13. The concentration of zinc in mineral waters (μg/L).
Figure 13. The concentration of zinc in mineral waters (μg/L).
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Table
Table 1. Values of the concentration of potassium 40K and radium 226Ra activity together with the results of statistical analysis.
Table 1. Values of the concentration of potassium 40K and radium 226Ra activity together with the results of statistical analysis.
Concentration of Activity (mBq/L)
Name40K 226Ra
Amita348 ± 2632.6 ± 9.4
Franciszek468 ± 329.5 ± 8.5
Henryk345 ± 268.3 ± 2.0
Józef370 ± 278.5 ± 6.2
Józefowianka407 ± 29<LLD
Laguna391 ± 2824.6 ± 9.1
Nałęczowianka151 ± 159.0 ± 8.6
Primavera288 ± 2210.0 ± 8.7
Słotwinka378 ± 27<LLD
Ustronianka355 ± 2612.8 ± 8.7
Zuber398 ± 28<LLD
Żywiecki-Kryształ379 ± 2718.3 ± 8.8
min151 ± 15<LLD
max469 ± 3232.6 ± 9.4
average357 ± 2614.8 ± 7.78
standard deviation74.2 ± 3.98.1 ± 2.2
median374 ± 2710.0 ± 8.7
coefficient of variation0.21 ± 0.150.55 ± 0.28
Table
Table 2. Average annual effective doses of 40K potassium uptake in drinking water in the tested mineral water samples.
Table 2. Average annual effective doses of 40K potassium uptake in drinking water in the tested mineral water samples.
Age Group<1 Year1–10 Years11–17 YearsAdults
40K
Conversion factor (μSv/Bq)6.2 × 10−22.8 × 10−27.6 × 10−20.62 × 10−2
Annual water consumption (L)250350540730
Annual effective dose (μSv/a)
Amita5.40 ± 0.403.42 ± 0.251.43 ± 0.111.58 ± 0.12
Franciszek7.26 ± 0.504.59 ± 0.311.92 ± 0.132.12 ± 0.15
Henryk5.35 ± 0.403.38 ± 0.251.42 ± 0.101.56 ± 0.12
Józef5.73 ± 0.423.62 ± 0.261.52 ± 0.111.67 ± 0.12
Józefowianka6.31 ± 0.443.99 ± 0.281.67 ± 0.121.84 ± 0.13
Laguna6.06 ± 0.433.83 ± 0.271.60 ± 0.111.77 ± 0.13
Nałęczowianka2.35 ± 0.241.48 ± 0.150.62 ± 0.060.69 ± 0.07
Primavera4.47 ± 0.352.83 ± 0.221.18 ± 0.091.31 ± 0.10
Słotwinka5.85 ± 0.423.70 ± 0.271.55 ± 0.111.71 ± 0.12
Ustronianka5.49 ± 0.403.47 ± 0.251.45 ± 0.111.60 ± 0.12
Zuber6.16 ± 0.443.90 ± 0.281.63 ± 0.121.80 ± 0.13
Żywiecki-Kryształ5.88 ± 0.423.72 ± 0.271.56 ± 0.111.72 ± 0.12
Table
Table 3. Average annual effective doses of 226Ra uptake in drinking water in the tested mineral water samples.
Table 3. Average annual effective doses of 226Ra uptake in drinking water in the tested mineral water samples.
Age Group<1 Year1–10 Years11–17 YearsAdults
226Ra
Conversion factor (μSv/Bq)4.700.791.500.28
Annual water consumption (L)250350540730
Annual effective dose (μSv/a)
Amita38.31 ± 11.059.01 ± 2.6026.41 ± 7.616.66 ± 1.92
Franciszek11.16 ± 9.992.63 ± 2.357.70 ± 6.891.94 ± 1.74
Henryk9.75 ± 2.352.29 ± 0.556.72 ± 1.621.70 ± 0.41
Józef9.99 ± 7.292.35 ± 1.716.89 ± 5.021.74 ± 1.27
Laguna28.91 ± 10.696.80 ± 2.5219.93 ± 7.375.03 ± 1.86
Nałęczowianka10.58 ± 10.112.49 ± 2.387.29 ± 6.971.84 ± 1.76
Primavera11.75 ± 10.222.77 ± 2.418.10 ± 7.052.04 ± 1.78
Ustronianka15.04 ± 10.223.54 ± 2.4110.37 ± 7.052.62 ± 1.78
Żywiecki-Kryształ21.50 ± 10.345.06 ± 2.4314.82 ± 7.133.74 ± 1.80
Table
Table 4. Average annual effective doses of the uptake of 232Th in drinking water in the Franciszek sample.
Table 4. Average annual effective doses of the uptake of 232Th in drinking water in the Franciszek sample.
Age Group<1 Year1–10 Years11–17 YearsAdults
232Th
Conversion factor (μSv/Bq)4.600.380.250.23
Annual water consumption (L)250350540730
Annual effective dose (μSv/a)
Franciszek2.76 ± 2.420.32 ± 0.280.32 ± 0.280.40 ± 0.35
Table
Table 5. Average annual doses effective for adults from uptake with drinking water in mineral water samples.
Table 5. Average annual doses effective for adults from uptake with drinking water in mineral water samples.
LocalityEffective Dose Rate (µSva−1)
Poland3.92 ± 1.34
Japan [54]5.6
Portugal [55]4.27
Turkey [56]4.62
Iran [57]150
World [58]290
Table
Table 6. The concentration of heavy metals in mineral water samples (µg/L).
Table 6. The concentration of heavy metals in mineral water samples (µg/L).
Concentration of Heavy Metals in Mineral Water Samples (µg/L)
NamePbCdCrCuNiHgZn
Amita12.51.68.0134.89.71.4288
Franciszek5.20.63.4118.84.50.6600
Henryk8.91.15.8347.56.40.2983
Józef12.00.722.5129.818.40.4325
Józefowianka37.01.917.0183.331.80.3528
Laguna14.61.53.6181.83.61.0983
Nałęczowianka13.90.78.045.318.80.31300
Primavera8.10.74.878.54.50.5373
Słotwinka39.82.846.8400.037.00.2993
Ustronianka15.20.711.053.57.40.1150
Zuber41.81.012.1195.515.70.1313
Żywiecki-Kryształ10.50.821.731.35.50.4323
min5.20.63.431.33.60.1150
max41.82.846.8400.037.01.41300
average18.31.213.7158.313.60.5596
standard deviation12.60.611.8110.310.70.4357
median13.20.99.5132.38.60.4450
coefficient of variation0.70.50.90.70.80.80.6
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Wojtkowska, M.; Wojtkowski, K.; Długosz-Lisiecka, M. Assessment of Heavy Metals and Radionuclides Concentration in Selected Mineral Waters Available on the Polish Market. Appl. Sci. 2022, 12, 11401. https://doi.org/10.3390/app122211401

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Wojtkowska M, Wojtkowski K, Długosz-Lisiecka M. Assessment of Heavy Metals and Radionuclides Concentration in Selected Mineral Waters Available on the Polish Market. Applied Sciences. 2022; 12(22):11401. https://doi.org/10.3390/app122211401

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Wojtkowska, Małgorzata, Karol Wojtkowski, and Magdalena Długosz-Lisiecka. 2022. "Assessment of Heavy Metals and Radionuclides Concentration in Selected Mineral Waters Available on the Polish Market" Applied Sciences 12, no. 22: 11401. https://doi.org/10.3390/app122211401

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