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Advances in Environmental Biology
Advances in Environmental Biology, 8(1) January 2014, Pages: 56-65 AENSI Journals Advances in Environmental Biology Journal home page: http://www.aensiweb.com/aeb.html Environmental Hydrochemistry and Seasonal Variations in Radon Concentration in Geno Hot Spring, North of Hormozgan, Iran 1 S.M. Mirhosseini, 2F. Moattar, 3A. Negarestani, 4A.R. Karbasi 1,2 Department of Environmental Science, Graduate School of the Environment and Energy, Science and Research Branch, Islamic Azad University- Tehran- Iran. 3 Kerman Graduate University of Technology, Kerman, Iran. 4 Graduate Faculty of Environment, University of Tehran, Tehran, Iran ARTICLE INFO Article history: Received 22 October 2013 Received in revised form 14 January 2014 Accepted 20 January 2014 Available online 1 March 2014 Key words: Geno hot spring, Hydrochemistry, Geothermometer, Radon. ABSTRACT Geno hot spring is one of the famous hot springs and hydrotherapy centers in Iran which has been used since ancient times. The spring is located on the eastern edge of anticline of double plunges of Geno from the series of Zagros folded corrosion. The average water temperature in Geno hot spring is 41/22 ° C and releases a strong odor of hydrogen sulfide due to sulfate rduction. The water type is sodium chloride (Na-Cl) due to the outcrop of salt domes of Hormuz Series, possible flow of water at great depth and flows back to the surface. The water is in a relative maturity and has reached a rather equilibrium with its rock repository. Weak correlation between magnesium and chloride ions in the samples of Geno hot spring can be the result of mixing of surface waters with deep brine. The water is saturated toward aragonite, calcite and dolomite and is under saturated toward phases such as gypsum, halite and anhydrite. Water temperature in the reservoir of Geno hot spring is estimated to be 55 to 1540 C based on geothermometer surveys. Radon concentration in water of Geno varies between 17.75 and 46.30 kBq/m3 throughout the year, so this spring is not a radon hot spring. © 2014 AENSI Publisher All rights reserved. To Cite This Article: S.M. Mirhosseini, F. Moattar, A. Negarestani, A.R. Karbasi., Environmental Hydrochemistry and Seasonal Variations in Radon Concentration in Geno Hot Spring, North of Hormozgan, Iran. Adv. Environ. Biol., 8(1), 56-65, 2014 INTRODUCTION One of the most common and most interesting tourist attractions is hot and mineral water springs in Iran, which are scattered in many different areas of the country. Some of these springs are very well known due to not only visual attractions but also their traditional use for washing, bathing and treatment of some diseases, but others are less known or unknown. In general, there is no uniform and accepted definition for hot spring and the term, hot spring, is used in different countries and sources in various forms. Some of these definitions are: Any geo-thermal spring [41]. Spring in which the water temperature is higher than room temperature (Miriam-Webster Online Dictionary, 2004). A spring in which the water temperature is higher than the average temperature of the human body that is 36.5 ° C [43]. A spring in which the water temperatures is higher than 36.7°C [44]. Any natural springs where the temperature is greater than 21.1oC [23]. NOAA defines warm spring as each spring with water temperatures of 20 to 50oC. Most hot springs are also mineral water spring, i.e. the concentration of their minerals is unusual or the kind of their minerals is unusual or special. Many researches were conducted on geochemistry of hot and thermal spring around the world aiming at determining the source of water, exploration of geothermal resources, and identification of mineral reserves, tectonic and geo-structural analysis, environmental and tourism studies, and monitoring and studying volcanic activities and so on. Studying dissolved gases and radioactive materials such as noble gas of radon were considered in many researches on studying hydro-chemicals of hot springs due to numerous reasons including the relationship of hot springs with faults and volcanic regions and origination of water from great depth as well as environmental effects. Radon is a radioactive, colorless, odorless and tasteless noble gas which is naturally obtained from the decay of uranium and thorium. 39 isotopes were identified from radon (193Rn and 231Rn); But radon is often seen as three naturally-occurring isotopes, every one of which are derived from different decay chains [13]. 222Rn Corresponding Author: S.M. Mirhosseini, Department of Environmental Science, Graduate School of the Environment and Energy, Science and Research Branch, Islamic Azad University- Tehran- Iran. E-mail: [email protected] 57 S.M. Mirhosseini et al, 2014 Advances in Environmental Biology, 8(1) January 2014, Pages: 56-65 isotope is more important than different isotopes of radon and is considered in environmental issues. When we talk about radon in many resources 222Rn is considered and two other isotopes are known in the name of Torun and Actinon. 222Rn isotope has enough time to remain in the weather of human environment due to half -life of 3.8 days and causes some threats for human health including lung cancer. Although, the position and health effects of hot and mineral springs in various region of Iran have been mentioned in some sources a few hundred years ago, scientific and more accurate studies on these waters started since the second half of the nineteenth century mainly by tourists and foreign scientists. More than 469 hot and mineral springs have been identified in Iran based on different studies and the provinces of Azerbaijan Gharbi, Ardebil, Mazandaran, Kerman and Sistan and Baluchistan have the most wellknown hot springs (Fig. 1). Fig. 1: Number of known hot springs in different provinces of Iran. There are many hot springs in Hormozgan province due to special geological features including being located in the Folded Zagros and comprising salt domes. 24 hot springs has been detected in Hormozgan province based on reviewing resources, some of which have been faced with charging reduction or the overall drying for various reasons in recent years. While there is not a single point as water exit in some above mentioned springs, there are separate embodiments which can be considered as independent springs. Furthermore, due to the variation in salt domes in the province and the relationship of many hot springs with the domes, there are probably many springs that are either unknown or only local people aware of their existence and there is no information in official sources. The most important hot springs in Hormozgan are: Geno,Khamir (Lashtan), Khorgo, Niyan, Chah Ahmad, Todrouye, Khoonsorkh( Chestane), Fotouye, Siyah kosh, Sangouye, Saye Khosh and Sargaz. Geno hot spring is the most famous spring in Hormozgan province that has been used for many years. John Fryer, English physician, talked about two bathhouses along with Geno hot spring in Bandar Abbas in the report of his visit to Iran in 1677, one of which was built by German and the other was built by the investment of an Indian banker and had been used in treating diseases. This spring is located at a distance of 33 km from North East Bandar Abbas, along with Bandar Abbas-Sirjan highway (Fig. 2-9). Now, the spring has turned into an Iranian popular hydrotherapy center in recent years due to proper investment, healthy indoor pools with other health care, recreational and accommodation facilities. The water spring was entered initially in an indoor small basin, and then much of it is directed toward public pools. Geno hot spring has an acceptable discharge with respect to the relatively high passenger volumes, and despite the relatively low flow rate than the past decade, the average annual rate is usually 100 to 150 liters per second. The weather is hot and humid in the region, the average annual rainfall is less than 100 mm, the average annual maximum and minimum temperatures is, respectively, 32.6 and 21.9°C and the average relative humidity varies between 45 to 75%. MATERIALS AND METHODS The spring water were sampled in containers made of polyethylene and with standard methods in four stages and during different seasons in 2012 (winter 2012 to fall 2013) to review the hydro-chemical traits of Geno hot spring. Samples were taken in two separate bottles and were sent to the laboratory, one was used to test anions and the other was used to test cations after adding a few drops of compound nitric acid to reach a pH of less than 2 in order to avoid possible oxidation reactions, adsorption and precipitation of some cations and reduce or prevent the growth of bacteria. Physical and chemical agents such as EC, pH and temperature were measured by portable devices at sampling site. Chemical analysis was performed in Australia Amdel Laboratory 58 S.M. Mirhosseini et al, 2014 Advances in Environmental Biology, 8(1) January 2014, Pages: 56-65 and Laboratory of Geological Survey of Iran. Major cations, metal elements and trace elements and some anions measured by Inductively Coupled Plasma (ICP) Method and anions measured by titration, atomic absorption and flame photometry methods. Measurement accuracy was approximately 3.4% based on the analysis of duplicate samples. Analysis Reliability was obtained using anion-cation balance, the difference between the total concentration of anions and cations were between 0.66 to a maximum of 4.96 %. Fig. 2: The changes of discharge of Geno hot spring over the past 4 decades (Hormozgan Regional Water Organization, 1970-2012). PhreeQC, AQqa and SPSS software were used to analyze the results after modification of sensor data. The concentration of radon (222Rn) was measured in the location of sampling by active radon detector of RAD7 at each stage of the sampling. The measurement accuracy by the detector was 1kBq/m3. Discussion: Geological situation: The main manifestation of the Geno hot spring is located in the eastern margin of Geno double plunge anticline in a coordinates of X: 431213 Y: 3036076 UTM. Geno anticline is of the series of folded Zagros with roughly east-west trending, rock units from old to new included Khami Group with the age of Upper Jurassic composed of limestone, shale, dolomite limestone and anhydrite, Bangestan Group included shale and limestone with the age of Cretaceous, Asmari-Jahrum Formation with the age of Eocene- Oligocene composed of limestone and dolomite limestone, Gachsaran, Razak and Mishan with the age of Miocene consisting of marl, anhydrite, sandstone and marl limestone, and Aghajari Formation with the age of Pliocene included sandstone and red marl. In addition, outcrop of Hormuz series can be seen in the eastern edge of the anticline and near Geno hot spring with the age of Infra Cambrian composed of salt and gypsum evaporation units as well as red soil (fig. 3). Hydrochemistry: Chemical composition and quality of groundwater is the result of processes and reactions performed during the formation and density of water in atmosphere until when it appears on the surface based on Todd [39] definition. Fetter [12] believes that the quality of ground water is the result of natural physical and chemical conditions of water and changes made by human activities. Various chemical reactions occur consistently and continually between ground water, substances in it and aquifer media. These reactions affect ultimately the quality of ground water and control water chemistry. Furthermore, these reactions can typically affect the transfer of substance in groundwater. The presence of evaporative rock units with high solvability and erosion in Hormoz Formation and salt domes are the major reason of salinity of ground water resources in western and central parts of Hormozgan. Geno hot spring and mineral water spring is a fault spring which is heavily affected by the above-mentioned outcrops. 59 S.M. Mirhosseini et al, 2014 Advances in Environmental Biology, 8(1) January 2014, Pages: 56-65 1. Alluvial deposits in the present covenant, 2. Old fan deposit and unfolded conglomerates, 3. Bakhtyari Formation: Conglomerate, Sandy marly Conglomerate, 4. Mishan Formation: Gray Marl, 5. Guri Member: Limestone, 6. Razak Formation: sandstone, Marl sandy Limestone, 7. Asmari-Jahrom Formation: Limestone, Dolomitic Limestone, 8. Pabdeh-Gurpi Formations: Calcareous Shale, gray marl, 9. Bangestan Group: Bituminous Shale, Limestone, 10. Khami Group: Limestone, shale, Anhydrite, 11. Hormoz Series: Salt Diapirs with gypsum and red oxides, 12. Landslip, 13. Fault, 14, Geno thermal Spring 15. Main road. Fig. 3: Geological map of the eastern part of the Geno anticline (from geological maps of Bandar Abbas, Iranian National Oil Company, 1994). Mineral water is classified differently in terms of temperature; one of the most important classifications is as follows: Very hot water above 45 o C, Hot water, 35 - 45 o C, Semi-hot water, 28 - 35 o C, Moderate water, 23-28 o C, Cold water, under 23 o C. The average of water temperature of Geno hot spring is 41.22 o C which has little changes during the year. Joneydi reported the degree of 41 o C for the spring water. The average annual discharge was more than 150l/s based on statistics, and discharge of the spring was more than 200 l/s in 70 and 80 decades (fig. 2). The most important traits of the spring observed in most hot spring of Hormozgan (including todrouye and Khoonsorkh) in Boshehr and south Iran, is the relatively strong smell of hydrogen which is mainly due to the reduction of sulfate (it has high concentration in ground water due to the presence of gypsum in salt domes and a series of Hormuz). Generally, the following two reactions can be effective in generating H2S in groundwater: 2CH2O+SO42SO4 (S) + CnHm (L) 2HCO3- +H2S CO2 (G) + H2O(L) + H2S The reduction of sulfate can be done by organic matter in the first reaction and bacteria act as a catalyst; the reaction in water resources occurs with non- oxidants-environment and it depends on the availability of reactive organic matter and sulfate resources. There is an exothermic reaction in the second reaction occurs from the contact of oil fluids with sulfated rock units [27]. It seems that the reaction is effective in producing heat and the foul-smelling gas of hydrogen 60 S.M. Mirhosseini et al, 2014 Advances in Environmental Biology, 8(1) January 2014, Pages: 56-65 sulfide in Geno hot spring. Although liquid droplets of oil found rarely in Geno hot spring, this phenomenon is frequently observed in Khorgo Sargaz springs that are not far behind Geno spring. Sodium cation (average concentration of 2892 milligrams per liter) and chloride anion (average concentration of 4892 mg l) are abundant ions in Geno hot spring based on the results of chemical analysis and the measurement in sampling location and the total amount of dissolved salts (TDS) varies between 8,770 to 13,600 milligrams per liter. Furthermore, the total amount of solutes shows high correlation between temperature and conductivity (average of 17,417 μs / cm) (Fig. 4). The position of samples of Geno hot spring in the Piper diagram and Steph diagrams of studied samples have been shown in figure 5. The water type is sodium chloride (Na-Cl) based on the diagrams, which is not unexpected due to the outcrop of salt domes of Hormuz Series, possible flow of water at great depth and flows back to the surface. In general, groundwater salinity increases with increasing depth and geochemical sequences in groundwater systems are as the shallow carbonates waters change to chloride water in great depth [39]. Fig. 4: Linear relationship between the total amount of water minerals and temperature and electrical conductivity of water in Geno hot spring. Fig. 5: Steph diagrams and the situation of samples of Geno hot spring in Piper diagram. In general, the composition of warm waters based on the classification of Werner and Giggenbach [17] are as follows: High acid-sulphate water: these waters are the result of dissolution of magmatic gases in groundwater being close to ISO chemical solubility in contact with the host rock, indicating deep internal conditions and imbalance. Sodium spring reflects the water with high reactivity of CO2 in the hydrothermal systems. Deep geothermal waters as “neutral chloride springs “that reach equilibrium with host rocks during rising. The situation of Geno hot spring samples in Giggenbach Na-k-Mg triangular diagram (Fig. 6) indicated that the waters source are in a relative maturity and has reached a rather equilibrium with its reservoir rock. The 61 S.M. Mirhosseini et al, 2014 Advances in Environmental Biology, 8(1) January 2014, Pages: 56-65 correlation of some cations and anions in groundwater can confirm mixing of surface and underground waters and can ensure that they are not mixing. For instance, linear relationship of chloride and magnesium shows nonoccurrence of mixing phenomenon [30]. It seems that the phenomenon of mixing with surface waters is not a significant component in the hot springs associated with salt domes in such area due to the high correlation of concentration of chloride and magnesium ions in about 20 samples of Hormozgan hot spring (including Fotouye, Todrouye, Ghachin, Sangouye, Geno); however, the correlation in Geno samples source was weakly shown, can be the result of mixing of surface waters with deep brine (Figure 7). Low concentration of boron (B /Cl), i.e. 0.00047 can also confirm the dilution of deep water near surface as well as poor leaching of boron in host rocks [35]. The correlation coefficient of measured parameters in Geno hot spring is given in Table 1. High correlation of concentrations of sodium and iron (0.912) and positive correlation of chlorine and sodium are some significant correlations which confirm the common origin of supplying these ions, Hormuz Series (horizon 1: Hormuz Series consists of thick salt layer and horizon 2: Hormuz Series consists of iron deposits, red oxides and hematite). The high correlation between the concentration of calcium and magnesium (0.927) can also be derived from a common origin of these elements, i.e. sequence of limestone and dolomite elements in Geno anticline. Fig. 6: Na-K-Mg triangular diagram to show the maturity status of waters (Giggenbach, 1988). Fig. 7: Correlation between magnesium and chloride concentration in West Hormozgan hot springs (right) and Geno hot spring (left). 62 S.M. Mirhosseini et al, 2014 Advances in Environmental Biology, 8(1) January 2014, Pages: 56-65 Table 1: Correlation matrix of measured parameters in water samples of Geno hot spring. Ca Mg Na K HCO3 CO3 SO4 Cl TDS EC pH T Sr Fe 1 0.927 0.311 0.328 -0.75 0.446 0.163 -0.46 -0.82 -0.56 0.185 -0.9 -0.84 0.662 Ca 1 0.644 0.304 -0.94 0.543 -0.13 -0.13 -0.58 -0.23 0.446 -0.99 -0.58 0.888 Mg 1 0.021 -0.85 0.397 -0.6 0.649 0.237 0.575 0.806 -0.67 0.253 0.912 Na 1 -0.09 0.926 -0.55 -0.5 -0.53 -0.49 -0.56 -0.38 -0.32 0.058 K 1 -0.42 0.246 -0.23 0.255 -0.12 -0.72 0.931 0.278 -0.99 1 -0.72 -0.23 -0.42 -0.26 -0.21 -0.63 -0.22 0.41 HC O3 CO3 1 -0.44 -0.33 -0.45 -0.09 0.231 -0.51 -0.33 SO4 1 0.883 0.994 0.745 0.111 0.841 0.342 Cl 1 0.928 0.389 0.557 0.973 -0.14 TDS 1 0.669 0.211 0.895 0.242 EC 1 -0.41 0.268 0.767 pH 1 0.532 -0.89 T 1 -0.15 Sr 1 Fe Reviewing saturation indices: PhreeqC software was used to determine molality, activity and saturation index of anions and cations of Geno hot spring, the results are given in Table 2. The results showed that the spring water is supersaturated towards phases of aragonite, calcite and dolomite and is under-saturated towards phases such as gypsum, halite and anhydrite. The mineralogical phase analysis (XRD) of sediment samples taken from a channel also indicated that calcite and dolomite are the main phase in the sediments of Geno hot spring. Table 2: Saturation index, molality and activity of different mineral phases in Geno hot spring. Phase SI log IAP log KT Anhydrite -0.91 -5.37 -4.47 Aragonite 0.12 -8.34 -8.46 Calcite 0.25 -8.34 -8.59 Celestite -0.37 -7.06 -6.69 Chalcedony -1.67 -5.04 -3.37 CO2(g) -1.92 -20.07 -18.15 Dolomite 0.39 -17.06 -17.45 Gypsum -0.78 -5.38 -4.60 Halite -3.64 -2.03 1.62 O2(g) -33.37 44.59 77.95 Quartz -1.29 -5.04 -3.75 CaSO4 CaCO3 CaCO3 SrSO4 SiO2 CO2 CaMg(CO3)2 CaSO4:2H2O NaCl O2 SiO2 Geothermometry: The main use of chemical geothermometry is estimation of reservoir temperature before reaching the cooling district. When we used this geothermometer, we always assumed that no significant changes occurred in the chemical composition of water and possible boiling may be considered as adiabatic [24]. Geothermometry (Ground temperature measurement) of Geno hot spring was performed based on Fournier, [14], Henley et al., [20], Kharaka and Mariner, [25] and Karingithi, [24] (Table 3). Two geothermometers of Na-K-Ca-Mg and Na-K did not show an identified temperature and the average temperature obtained from Na-K-Ca was 153.39 oc. Karingithi [24] believed that using Na-K geothermometer is not appropriate for waters with high calcium concentration and reservoir temperature of less than 150 ° C and high concentrations of magnesium lead to unusual high temperatures in Na-K-Ca-Mg geothermometer. Na-KCa geothermometer was more suitable for water with high calcium and using for cold water or hypothermal as well as immature hydrothermal did not lead to misdiagnosis and or unusual high temperature [14,24]. Furthermore, the results of other geothermometer are more acceptable for Geno hot spring. Moreover, the results of different geothermometer in hydrothermal systems with low to moderate temperatures (50 to 150 ° C) should always be considered cautiously; water temperature in the reservoir of Geno hot spring estimated to be 55 to 154 ° C. Certain geological situations and certain hydrological conditions such as the abundance of evaporate and carbonate rock units, mixing of waters and also disequilibrium of groundwater with reservoir rock are reasons for failure to obtain similar results in applying different geothermometer. 63 S.M. Mirhosseini et al, 2014 Advances in Environmental Biology, 8(1) January 2014, Pages: 56-65 Table 3: Results of geothermometry of Geno hot spring samples in different seasons. GN1 GN2 GN3 GN4 Temperature average Quartz(max esteam loss) 45/293 56/262 72/167 51/893 56/43 Quartz (No esteam loss) 52/716 62/555 76/677 58/646 62/64 Na-K 150> 172/28 150> 150> - Na-K-Ca 151/9 173/98 146/81 140/87 153/39 Na-K-Ca-Mg 350< 350< 350< 350< - Mg-Li 78/964 84/333 79/66 77/132 80/02 Na-Li 120/56 131/07 124/27 115/83 122/93 Radon concentration in the water of Geno hot spring: Radon entered underground water from two possible sources: - Radioactive decay of radium solution - Direct release of radon from uranium and thorium -bearing minerals present in the rock underground reservoir Uranium and thorium -bearing minerals has much more contribution from two above-mentioned factors and the primary source can be ignored in many cases. Generally, concentrations of radon in groundwater is largely dependent on factors such as hydrodynamic factors, geothermometric factors, uranium in reservoir rock, kinds of minerals containing uranium and thorium, availability of release of radon gas and concentration of dissolved radium in water [33,32,6,3]. Since several anomalies of uranium or thorium found in salt domes in south Iran and minerals containing uranium can be exploited in some cases such as Gachine salt dome; there are always such environmental concerns related to the concentration of uranium, thorium, and also radon concentration in hot springs associated with salt domes. Measurements performed at the four seasons (Winter 2011, Spring, Summer and Fall 2012) showed the concentrations of radon gas to be 17.75 to 46.30 kBq/m3 (Table 4). Differences of concentrations recorded at different times in different regions of active tectonics (including Geno anticlines) are not unexpected, the severe effect of the slightest movement of the ground on release of produced radon and reaching to the water sources. The concentration of radon gas in water should be more than 2 Nano Corey per liter (2nCi/L) equivalent to 74 kBq/ m3 to consider a mineral spring as radon mineral water spring from geochemical point of view (amtamassage.org, 2009). Since, the average concentration of Radon is 28.84 kBq/ m3 based on the measurements, Geno hot spring is not a radon mineral water spring. EPA standard for radon concentration in the springs water is 150 kBq/m3, and Geno hot spring does not have any special problem in this case and no danger threaten the patrons life due to the relatively good air conditioning in swimming pool. Comparison of the radon concentration of Geno hot spring with Sarein hot spring in Ardebil (9.7-139.8 Kb/m3 Karimdoust and Ardebili, [26] and Joshan spring in Kerman (45.5 Kb/m3, Montazeri et al., [29] originating from igneous rock repositories showed that the lithology of rock repositories and sedimentary in contact with water has the most important role in the concentration of radon in the water of each area. It should be noted that the maximum allowable concentration of uranium in groundwater and mineral water is 10-20 ppb based on the guidelines of the World Health Organization and the Environmental Protection Agency which varies between 0.015-1.91 ppb in the water of Geno hot spring. Table 4: Uranium, thorium and radon soluble in the water of Geno hot spring. U ug/L Winter 2011 0/17 Spring 2012 1/99 Summer 2012 0/24 Fall 2012 0/015 Th ug/L 222 Rn KBq/m3 0/05> 0/05> 0/05> 0/05> 17/75 31/47 19/87 46/30 64 S.M. Mirhosseini et al, 2014 Advances in Environmental Biology, 8(1) January 2014, Pages: 56-65 Conclusion: Geno is a fault springs with karst reservoir which is located on the eastern edge of the Geno anticline. Water type is sodium chloride (Na-Cl) due to the outcrop of salt domes of Hormuz Series, possible flow of water at great depth and flows back to the surface. The water is in relative maturity and has reached a rather equilibrium with its reservoir rock. Mixing water with some surface water seems likely due to the correlation of magnesium and other ions, and also low concentration of chloride to boron (B / Cl). The water has a relatively strong smell of hydrogen sulfide which more than anything else, is due to the reduction of sulfate. Measurement of saturation indices of different water phases and also XRF analysis of sediment samples showed that the spring water is supersaturated towards phases of aragonite, calcite and dolomite and is undersaturated towards phases such as gypsum, halite and anhydrite. Certain geological situations and certain hydrological conditions such as the abundance of evaporate and carbonate rock units, water mixing and also disequilibrium of groundwater with reservoir rock did not cause to obtain similar results in applying different geothermometer. Water temperature in the reservoir of Geno hot spring is estimated to be 55 to 1540 C considering the geochemical status of water. Annual changes in the concentration of radon gas in the spring water is 17.15 to 46.30 kBq/m3 which is less than EPA standard for radon concentration in springs water (150 kBq/m3) and no danger threaten the patron’s life due to the relatively good air conditioning in swimming pool. 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