The detailed analysis of natural radionuclides dissolved in spa waters of the Kłodzko Valley, Sudety Mountains, Poland

STOTEN-20322; No of Pages 16 Science of the Total Environment xxx (2016) xxx–xxx

Contents lists available at ScienceDirect

Science of the Total Environment journal homepage: www.elsevier.com/locate/scitotenv

The detailed analysis of natural radionuclides dissolved in spa waters of the Kłodzko Valley, Sudety Mountains, Poland A. Walencik-Łata a,⁎, B. Kozłowska a, J. Dorda a, T.A. Przylibski b a b

University of Silesia, Institute of Physics, Department of Nuclear Physics and Its Applications, Uniwersytecka 4 St., 40-007 Katowice, Poland Wrocław University of Technology, Faculty of Geoengineering, Mining and Geology, Division of Geology and Mineral Waters, Wybrzeże S. Wyspiańskiego 27, 50-370 Wrocław, Poland

H I G H L I G H T S

G R A P H I C A L

A B S T R A C T

• Description of radionuclides behavior in groundwater environment was presented. • 222Rn shows the highest concentration in shallow circulation groundwater. • 222Rn is independent on the concentration of dissolved 226Ra2 +. • 226Ra is dissolved in groundwater due to raised content in reservoir rocks. • Radiological risk was assessed from Rn, U, and Ra consumption with water.

a r t i c l e

i n f o

Article history: Received 16 April 2016 Received in revised form 14 June 2016 Accepted 24 June 2016 Available online xxxx Editor: F.M. Tack Keywords: Radon 222Rn Radium 226,228Ra Uranium 234,238U Effective dose radionuclide's behavior radionuclide's hydrochemistry

a b s t r a c t A survey was conducted to measure natural radioactivity in spa waters from the Kłodzko Valley. The main goal of this study was to determine the activity concentration of uranium, radium and radon isotopes in the investigated groundwaters. Samples were collected several times from 35 water intakes from 5 spas and 2 mineral water bottling plants. The authors examined whether the increased gamma radiation background, as well as the elevated values of radium and uranium content in reservoir rocks, have a significant impact on the natural radioactivity of these waters. The second objective of this research was to provide information about geochemistry of U, Ra, Rn radionuclides and the radiological and chemical risks incurred by ingestion of isotopes with drinking water. On the basis of results obtained, it is feasible to assess the health hazard posed by ingestion of natural radioactivity with drinking waters. Moreover, the data yielded by this research may be helpful in the process of verification of the application of these waters in balneotherapy. In addition, annual effective radiation doses resulting from the isotopes consumption were calculated on the basis of the evaluated activity concentrations. In dose assessment for uranium and radium isotopes, the authors provided values for different human age groups. The obtained uranium content in the investigated waters was compared with the currently valid regulations concerning the quality of drinking water. Based on the activity concentrations data, the activity isotopic ratios 234U/238U, 226Ra/238U, 222Rn/238U, 222Rn/226Ra and the correlations between radionuclides content were then examined. In brief, it may be concluded on the basis of the obtained results that radon solubility is inversely proportional to radium and uranium dissolution in environmental water circulation. The presented study allows conclusions to be drawn on the radionuclide circulation among different environmental biota: from lithosphere through hydrosphere to biosphere. © 2016 Elsevier B.V. All rights reserved.

⁎ Corresponding author. E-mail address: [email protected] (A. Walencik-Łata).

http://dx.doi.org/10.1016/j.scitotenv.2016.06.192 0048-9697/© 2016 Elsevier B.V. All rights reserved.

Please cite this article as: Walencik-Łata, A., et al., The detailed analysis of natural radionuclides dissolved in spa waters of the Kłodzko Valley, Sudety Mountains, Poland, Sci Total Environ (2016), http://dx.doi.org/10.1016/j.scitotenv.2016.06.192

2

A. Walencik-Łata et al. / Science of the Total Environment xxx (2016) xxx–xxx

1. Introduction To begin, detailed investigations of natural radioactivity in groundwater from spas: Polanica-Zdrój, Duszniki-Zdrój, Długopole-Zdrój, Kudowa-Zdrój, Lądek-Zdrój, as well as from mineral water bottling plants in Jeleniów and Szczawina were conducted. The investigated localities are situated in the Kłodzko Valley, in the Sudety Mountains, placed in the southwestern part of Poland (Fig. 1). The region of southwestern Poland, in particular the Sudety Mountains, is characterized by increased gamma radiation background (Isajenko et al., 2012). This is due to the geological structure of the area which belongs to the crystalline Bohemian Massif, the largest in Central Europe. The crystalline rocks building this massif, mostly gneisses, with enhanced levels of uranium concentrations, are present on the surface or just under a thin alluvium cover (Przylibski, 2005). Radium 226Ra isotope content in this massif which forms reservoir rocks for groundwater indicates unambiguously the elevated levels of this isotope in the Earth crust in the Sudety Mts. region in the south of Poland (Przylibski, 2004). According to Przylibski (2004), 226Ra activity concentrations in the reservoir rocks are in a range from 1 Bq/kg up to 224 Bq/kg, which strongly exceeds the average value (25.3 Bq/kg) or the typical range (3.7–143.7 Bq/kg) of this isotope in the surface layer of the Earth crust (Isajenko et al., 2012; Przylibski, 2005). The high values of 226Ra and its wide range dependent on the lithological type of rocks present in the Sudety Mts. are the effect of the diversity and the occurrence of locally high concentrations of uranium in these rocks. Crystalline rocks of the Kłodzko Valley show the average values of uranium content equal to 3.94 ppm in the Kudowa granites and 4.18 ppm in the Kłodzko-Złoty Stok granitoides (Plewa and Plewa, 1992), reaching the highest value of 11.3 ppm in the Śnieżnik gneisses (Przeniosło, 1970). Moreover, the presence of uranium deposits and spots of uranic mineralisations was revealed in the Kłodzko Valley (Fig. 1). Some of these deposits, for instance the deposit in Kletno, were exploited at the beginning of the second half of the 20th century (Bareja et al., 1987; Borucki et al., 1967; Miecznik et al., 2011). The investigations of natural radioactive isotopes in groundwater of the Kłodzko Valley carried out so far referred mainly to radon 222Rn isotope and its parent nuclide 226Ra (Adamczyk-Lorenc, 2007; Ciężkowski and Przylibski, 1997; Kozłowska et al., 1999; Kozłowska et al., 2010a; Przylibski and Żebrowski, 1999; Przylibski, 2000b, 2005; Przylibski et al., 2002, 2004, 2014). Given that the waters from that region are not only used in balneotherapeutic treatments but are also consumed as bottled waters, the authors decided to perform complex studies of the presence of the most important natural radioactive isotopes dissolved in groundwater. Indeed, the obtained results are interesting not only from the hydrogeochemical point of view, but also for the purposes of radiological protection of the inhabitants, tourists and patients living in and visiting the Kłodzko Valley. Long lived 238,234U and 226,228Ra radionuclides are responsible for the natural radioactivity of groundwater. During the decay process of these isotopes, α and β as well as γ radiation is released. The largest contribution to the effective dose from the ionizing radiation resulting from radioactive decay of natural radionuclides dissolved in groundwater comes from 226,228Ra isotopes (Chau et al., 2011). Furthermore, an additional isotope which occupies a crucial role in the natural radioactivity of groundwaters is the gaseous isotope 222Rn. Exposure to high concentrations of radioactive noble gas radon (T1/2 = 3.82 d) may lead to lung cancer (IARC, 1988, 2001, 2012; Haque and Kirk, 1992; Lubin et al., 2004; Darby et al., 2001, 2005, 2006; Lubin, 2003; Krewski et al., 2005, 2006; Grosche et al., 2006; Tomášek et al., 2008). In case of radium ingestion, most of it is quickly excreted, however, a fraction enters the bloodstream and the bone tissue, and it may lead to bone cancer (IARC, 2001, 2012; Rowland et al., 1978, 1983; Spiers et al., 1983; Stebbings et al., 1984; Carnes et al., 1997; Leenhouts and Brugmans, 2000; Nekolla et al., 2000; Bijwaard et al., 2004; Wick et al., 2008). In addition, uranium ingestion from water and food and inhalation can

lead to cancer and kidney damage. Uranium is radiologically and chemically toxic and its chemical toxicity is predominant (WHO, 2011). The World Health Organization and the Environmental Protection Agency estimated the provisional guideline value for total content of uranium in drinking water to be equal to 30 μg/L (WHO, 2011; EPA, 2000). The characteristics of the studied intakes along with a short specification of the groundwaters are presented in Table 1. The investigated waters were recognized accordingly as acidulous (CO2 rich), thermal (T N 20 °C), mineral (TDS ≥ 1 g/L) or radon enriched (222Rn ≥ 74 Bq/L). Mainly, the deployment faults and deep fissures performed an essential role in natural water spring formation. Carbon dioxide coming from the great depth and translocating through faults and fissures was dissolved in water. These aggressive waters interacting with reservoir rocks received the mineralization up to 2–3 g/L (Ciężkowski, 1990). Then, groundwater transfluent through reservoir rocks characterized by elevated concentrations of 226Ra and higher emanation coefficient become radon enriched water. This is most often water of shallow circulation (Przylibski, 2000a, 2005, 2011). Deep circulation of infiltration water (due to the presence of faults and fissures) and its geothermal heating is the reason for the origin of thermal water (Ciężkowski, 1990; Zuber et al., 1995; Ciężkowski et al., 2011). In general, the investigated region is known for a large number of natural water springs. Waters containing pharmacodynamical agents are regarded as medicinal and are used for balneological purposes. Therapeutic effects of water from Lądek-Zdrój Spa has been known for N700 years (Ciężkowski, 1990). Moreover, some of the waters are bottled as mineral or medicinal waters and are distributed throughout the country and abroad. Some water intakes are available for free to local inhabitants and tourists coming there on holiday. It should be noted that the previous examinations indicated that the waters present in this area have a high radon concentration reaching N 1000 Bq/L (Adamczyk-Lorenc, 2007; Ciężkowski and Przylibski, 1997; Kozłowska, 2009; Kozłowska et al., 2010a; Przylibski, 2005; Przylibski and Żebrowski, 1999; Przylibski, 2000b, 2004; Przylibski et al., 2014). The investigation of radium and uranium isotopes in the groundwater intakes from the Sudety Mts. (Kozłowska, 2009; Przylibski et al., 2002, 2014; Walencik, 2010; Walencik et al., 2012) showed that the groundwaters, particularly from the Kłodzko Valley contain higher values of these elements than other waters in Poland, excluding some brines and thermal waters (Chau et al., 2012; Kozłowska et al., 2010b; Nowak et al., 2012). The goal of the present study was to determine the activity concentration of isotopes 222Rn, 226,228Ra, 234,238U, which are in essence of utmost importance from the point of view of radiological protection. On the basis of evaluated concentrations, the authors calculated the activity ratios 234U/238U, 226Ra/238U, 222Rn/238U, 222Rn/226Ra and studied the correlations between different isotopes and mineralization, as well as the depth of intakes and the depth of shallow circulation waters. The second aim of this study was to provide information on the radiological and chemical risks resulting from ingestion of these isotopes with drinking water. This problem is indeed socially important in countries like Poland, where medical water is freely available for consumption. The uranium content in the investigated water intakes was compared with the currently valid regulations concerning the quality of drinking water. The authors assessed doses from isotopes consumption with drinking waters. The present studies completed the existing data base of the results. This allowed for a deeper understanding of the hydro-geochemistry of the studied region and the assessment of the overall radiological impact on local inhabitants in different age groups living in an extended period of time in this region. 2. Materials and methods 2.1. Sampling Sample collection was performed several times over a period of 15 years from 35 water intakes from 5 spas and 2 mineral water bottling

Please cite this article as: Walencik-Łata, A., et al., The detailed analysis of natural radionuclides dissolved in spa waters of the Kłodzko Valley, Sudety Mountains, Poland, Sci Total Environ (2016), http://dx.doi.org/10.1016/j.scitotenv.2016.06.192

A. Walencik-Łata et al. / Science of the Total Environment xxx (2016) xxx–xxx

3

Fig. 1. A simplified geological map of the Kłodzko Valley (after Sawicki, 1966, 1995) covering locations of spas and mineral water bottling plants with investigated groundwaters. Uranium deposits and mineralization points are marked according to the map compiled by Przylibski (2005). Localization of the Kłodzko Valley, the area of research, is also presented on the tectonic map of the sub-Cenozoic surface of Poland, except the Alpine units of the Carpathians and the Carpathian foredeep (according to (Znosko, 1998; Narkiewicz and Dadlez, 2008; Karnkowski, 2008)) with a slightly modified and standardized division into the main tectonic units. The Sudetes and the Fore-Sudetic block form the Lower Silesian block is the only radon-prone area in Poland.

Please cite this article as: Walencik-Łata, A., et al., The detailed analysis of natural radionuclides dissolved in spa waters of the Kłodzko Valley, Sudety Mountains, Poland, Sci Total Environ (2016), http://dx.doi.org/10.1016/j.scitotenv.2016.06.192

4

A. Walencik-Łata et al. / Science of the Total Environment xxx (2016) xxx–xxx

Table 1 Characteristics of investigated groundwaters (after (Przylibski, 2005) and author's unpublished data).

Spa or bottling plant

Brand name of intake

Type of water

Depth [m b.g.l.] TDS (intake/infiltration [mg/L] water circulation)

Polanica-Zdrój

P-300/P-300a

HCO3-Ca-Na

2634

221/32

Józef Stary Pieniawa Józefa I Pieniawa Józefa II Wielka Pieniawa

HCO3-Ca HCO3-Ca HCO3-Ca HCO3-Ca

1760 1217 799 1493

n.d./30 88.9/38 43/17 31.5/30

Jan Kazimierz

HCO3-Ca-Na

1567

162/12

B-1 B-2 (Agata) B-3 (Jacek) B-4 Pieniawa Chopina

HCO3-Ca-Na-Mg HCO3-Ca-Na-Mg HCO3-Ca-Mg HCO3-Ca-Na-Mg HCO3-Ca-(Na)

2492 1147 1195 2720 2182

33/13 91/18 96/12 56/30 78/21

No. 39

HCO3-Ca-Na-Mg

1907

180/60

Zimny Zdrój Studzienne

HCO3-Ca-Mg HCO3-Ca-Mg

942 696

34/14 8/30

Długopole-Zdrój Emilia

HCO3-Ca-Mg

910

18/30

Renata

HCO3-Ca-Mg

1218

16.6/30

Kazimierz

HCO3-Ca-Mg

937

27.1/30

K-200 No. 2 Moniuszko

HCO3-Na-Ca HCO3-Na-Ca

3342 3436

211/89 24/6

No. 3 (Nowy Marchlewski) Śniadecki Górne J-150 Sarenka No. 2 No. 5 No. 6 No. 7 Chrobry

HCO3-Na-Ca,

2127

15/2

HCO3-Na-Ca HCO3-Na-Ca HCO3-Na-Ca HCO3-Ca-Na HCO3-Ca-Mg HCO3-SO4-Ca-(Mg) HCO3-Ca-Mg HCO3-SO4-Ca-Mg HCO3–(CO3)-F-(SO4)-Na

3039 2456 1380 1921 421 257 369 294 201

18.3/5 4/30 98/20 n.d. n.d. 25 20/30 20/30 9.6/30

Dąbrówka

199

3.5/30

Jerzy

188

2/30

L-2 (Zdzisław)

208

700.5/97

Skłodowska-Curie

199

2/30

Wojciech

202

2/30

Duszniki-Zdrój

Szczawina

Kudowa-Zdrój

Jeleniów

Lądek-Zdrój

Pharmacodynamical agents [mg/L]a

Water description

Borehole, bottled “Staropolanka 2000” and “Saguaro” Borehole, not used currently Borehole, bottled “Staropolanka” Borehole, bottled “Staropolanka” Borehole, bathing and drinking therapy, drinking water of free access, bottled “Wielka Pieniawa” Fe (0.2–22.5), Si Borehole, bathing and drinking therapy, CO2 production (12.8–123), CO2 (50–2740), H2S (0.0–4.4) Borehole, currently not used Borehole, currently not used Borehole, drinking water of free access Borehole, CO2 production Borehole, drinking therapy, drinking water of free access, CO2 production Borehole, bathing and drinking therapy, CO2 production Borehole, currently not used Borehole, formerly bottled “Długopolanka”, Fe (8–26), CO2 (2144–2780) closed for reconstruction Fe 9–15, CO2 (826–2646) Intake in adit, drinking, bathing, inhalation therapy and drinking water of free access Intake in adit, drinking, bathing, inhalation therapy and drinking water of free access Intake in adit, drinking, bathing, inhalation therapy and drinking water of free access Fe (0.3–22), CO2 Borehole, drinking water of free access (1480–3190), H2S Borehole, drinking therapy and drinking (0.0–4.6) water of free access Borehole, drinking therapy and drinking water of free access Borehole, currently not used Well, bathing therapy Fe (0.3–12), CO2 (0–2440) Borehole, prepared for bottling Well, currently not used Borehole, bottled “Kudowianka” Well, bottled “Kudowianka” Well, bottled “Staropolanka Zdrój” Well, bottled “Staropolanka Zdrój” F (7–12.9), H2S (0.0–4.9), T Well, bathing, drinking therapy and drinking (18.7–4.7 °C) water of free access Well, bathing, drinking therapy and drinking water of free access Spring, bathing, drinking therapy and drinking water of free access Borehole, bathing, drinking therapy and drinking water of free access Spring, bathing, drinking therapy and drinking water of free access Spring, bathing therapy Fe (0.8–38), CO2 (535–2870), H2S (0.0–1.2)

n.d. – denotes no information was found in literature. a Pharmacodynamical agents are not present in all investigated groundwaters or are present temporarily (values of Fe, correspond to Fe2+, and values of Si correspond to H2SiO3).

plants (Fig. 1). The samples were collected in 5 L polyethylene bottles and then acidified in order to avoid radionuclide precipitation as well as adsorption on the walls of the containers. 2.2. Experimental procedures The measurements of radon 222Rn and radium 226,228Ra activity concentrations were performed with the use of the 1414 WinSpectral α/β liquid scintillation counter from Wallac. The activities of 222Rn were determined under the procedure established by Suomela (1993a). The samples were collected directly from boreholes, springs, or water intakes. A 10 mL water sample was drawn by means of a disposable syringe and then transferred to a scintillation vial filled with 10 mL scintillation coctail Insta – Fluor from Packard. The spectra were collected over a period of a

few days until total disintegration of radon occurred with measurements lasting 1800 s. The Minimum Detectable Activity (MDA) was calculated using Currie's method (Currie, 1968) and was equal to 1 Bq/L. A chemical procedure based on the POLISH NORM (1989) was applied in order to determine 226,228Ra isotopes in the investigated waters. This procedure involves preconcentration of radium by coprecipitation with BaSO4 and separation of radium from other radionuclides present in the waters. Measurements with LSC counter were performed once per day with 1 h counting time over a period of 25 days. Afterwards, a secular equilibrium between radium and its derivatives was reached and this allowed for consideration of theoretical Bateman curves for each radium isotope separately. Activity concentrations of 226Ra were calculated from α part of the spectrum, while 228Ra content was determined from a high – energy β spectrum originating from 228Ac being in an equilibrium

Please cite this article as: Walencik-Łata, A., et al., The detailed analysis of natural radionuclides dissolved in spa waters of the Kłodzko Valley, Sudety Mountains, Poland, Sci Total Environ (2016), http://dx.doi.org/10.1016/j.scitotenv.2016.06.192

A. Walencik-Łata et al. / Science of the Total Environment xxx (2016) xxx–xxx

state with 228Ra (Kozłowska, 2009; Walencik et al., 2010). MDA was equal to 0.01 Bq/L and 0.03 Bq/L for 226Ra and 228Ra, respectively, for 3600 s counting time and 2 L of water initial sample volume. The determination of 234,238U isotopes was performed with the use of α – spectrometers 7401VR (Canberra – Packard, USA) equipped with the Passivated Implanted Planar Silicon detectors with surfaces area of 300 mm2. At the start of each analysis, the standard 232U of known activity was added to a 0.5 L sample. The separation of uranium from other alpha isotopes was performed with the use of the anion exchange resin Dowex 1 × 8 (Cl− type, 200–400 mesh) on the basis of the procedure established by Suomela (1993b). A thin α source was prepared from uranium fraction by coprecipitation with NdF3 (Sill, 1987). Samples were measured over a period of 1–2 days. MDA was equal to 0.5 mBq/L for both 234,238U isotopes and 0.5 L initial sample volume. The chemical recoveries varied from 60% to 90%. 3. 3. Results and discussion 3.1. Activity concentrations and correlation investigations The results of the activity concentrations of 222Rn, 226,228Ra, 234,238U and uranium content are presented in Tables 2 and 3. The uncertainties were calculated as square roots of the sum of uncertainties in all quantities in quadrate. The presented results of all isotopes correspond to the arithmetic means from a few analytical results and the standard deviation of the mean. The activity concentrations of 222Rn varied in a range from 5 ± 1 Bq/ L to 1171 ± 87 Bq/L. The highest value was observed in the spring water Jerzy from Lądek-Zdrój Spa. According to the Przylibski (2005) classification, this water can be classified as high-radon water. The radon result

5

significantly higher than for other waters from Lądek-Zdrój Spa is due to the localization of the Jerzy spring in a close neighborhood of a fork of a huge dislocation zone and an increased emanation coefficient of weathered rocks (Przylibski and Żebrowski, 1999). The balneotherapy of radon as bathing in this spa was described elsewhere (Omulecki et al., 1996). A significant part of the exploited groundwaters from LądekZdrój Spa, Długopole Spa and Szczawina may be classified as radon waters (222Rn concentration between 100 and 999.99 Bq/L, Przylibski, 2005). According to the WHO (2011) recommendation, these waters should not be used for daily human consumption. The other waters may be classified among low – radon waters (222Rn between 10 and 99.99 Bq/L) and radon – poor waters (222Rn concentration between 1 and 9.99 Bq/L). The activity concentrations of radium varied from 0.010 ± 0.005 Bq/ L to 1.06 ± 0.06 Bq/L and from 0.01 ± 0.01 Bq/L to 0.33 ± 0.05 Bq/L for 226 Ra and 228Ra, respectively. All waters exhibited activity concentrations of 226Ra over MDA. Nine out of 35 water samples showed activity concentrations of 228Ra below MDA. The activity concentrations of uranium isotopes varied from 0.5 ± 0.2 mBq/L to 81 ± 4 mBq/L and from 0.7 ± 0.3 mBq/L to 239 ± 11 mBq/L for 238U and 234U, respectively. Three and one out of 35 investigated groundwaters show the activity concentrations below MDA for 238 U and 234U, respectively. Uranium content was evaluated on the basis of the activity concentrations. The highest value (Table 3) (6.3 ± 0.3 μg/L) was observed in water from Duszniki-Zdrój Spa. This water is available for free to local inhabitants. All the uranium concentrations in the investigated waters (Table 3) were significantly below the limit for drinking waters (b30 μg/L) established by the World Health Organization (2011) and the Environmental Protection Agency (2000).

Table. 2 Activity concentrations of 222Rn, 226,228Ra in [Bq/L] in investigated water samples from the Kłodzko Valley. Spa

Brand name of intake

222

Polanica-Zdrój

P-300 P-300a Józef Stary Pieniawa Józefa I Pieniawa Józefa II Wielka Pieniawa Jan Kazimierz B-1 B-2 (Agata) B-3 (Jacek) B-4 Pieniawa Chopina No. 39 Zimny Zdrój Studzienne Emilia Renata Kazimierz K-200 No. 2 (Moniuszko) No. 3 (Marchlewski) Śniadecki Górne J-150 Sarenka No. 2 No. 5 No. 6 No. 7 Chrobry Dąbrówka Jerzy L-2 (Zdzisław) Skłodowska-Curie Wojciech

5 ± 2 (4) 13.8 ± 0.7 (1) 23 ± 3 (3) 18 ± 2 (5) 21 ± 1 (5) 18 ± 1 (5) 17.5 ± 0.6 (5) 16 ± 5 (2) 54 ± 6 (2) 89 ± 2 (4) 5 ± 1 (4) 9 ± 1 (4) 10.1 ± 0.8 (4) 55 ± 1 (1) 117 ± 5 (1) 100 ± 13 (4) 70 ± 2 (4) 79 ± 15 (4) 8 ± 1 (4) 5.7 ± 0.6 (4) 66 ± 4 (4) 17 ± 1 (3) 20 ± 2 (3) 95 ± 22 (4) 26 ± 11 (2) 35 ± 10 (3) 39 ± 11 (3) 83 ± 19 (4) 73 ± 34 (2) 131 ± 8 (5) 136 ± 8 (5) 1171 ± 87 (5) 120 ± 3 (5) 325 ± 21 (5) 217 ± 7 (4)

Duszniki-Zdrój

Szczawina Długopole-Zdrój

Kudowa-Zdrój

Jeleniów

Lądek-Zdrój

Rn [Bq/L]

226

Ra [Bq/L]

1.01 ± 0.09 (4) 1.06 ± 0.03 (1) 0.17 ± 0.01 (3) 0.18 ± 0.01 (4) 0.12 ± 0.01 (4) 0.27 ± 0.02 (4) 1.01 ± 0.07 (4) 0.30 ± 0.20 (2) 0.07 ± 0.03 (2) 0.71 ± 0.04 (4) 0.97 ± 0.16 (3) 0.54 ± 0.1 (3) 0.56 ± 0.06 (3) 0.17 ± 0.08 (1) 0.092 ± 0.004 (2) 0.09 ± 0.01 (3) 0.10 ± 0.03 (3) 0.12 ± 0.01 (3) 0.64 ± 0.15 (3) 0.11 ± 0.03 (3 0.07 ± 0.01 (3) 0.21 ± 0.09 (2) 0.20 ± 0.09 (2) 0.38 ± 0.13 (3) 0.05 ± 0.02 (2) 0.02 ± 0.01 (2) 0.02 ± 0.01 (2) 0.04 ± 0.01 (3) 0.05 ± 0.04 (1) 0.010 ± 0.005 (3) 0.011 ± 0.006 (2) 0.089 ± 0.002 (18) 0.013 ± 0.004 (4) 0.027 ± 0.001 (12) 0.012 ± 0.001 (5)

228

Ra [Bq/L]

0.07 ± 0.02 (2) 0.16 ± 0.02 (1) 0.08 ± 0.06 (2) 0.05 ± 0.02 (4) 0.04 ± 0.01 (3) 0.04 ± 0.01 (4) 0.11 ± 0.01 (2) 0.18 ± 0.04 (1) 0.03 ± 0.04 (1) 0.24 ± 0.06 (4) 0.33 ± 0.05 (3) 0.28 ± 0.02 (3) 0.21 ± 0.05 (3) 0.06 ± 0.08 (1) 0.07 ± 0.01 (2) 0.03 ± 0.01 (2) 0.09 ± 0.03 (3) 0.05 ± 0.01 (3) 0.12 ± 0.05 (2) 0.11 ± 0.05 (3) 0.08 ± 0.01 (2) 0.07 ± 0.04 (2) 0.05 ± 0.01 (1) b0.03 0.01 ± 0.01 (1)⁎ b0.03 b0.03 b0.03 0.03 ± 0.01 (1) b0.03 b0.03 b0.03 0.013 ± 0.003 (1)⁎ b0.03 b0.03

For 222Rn and 226,228Ra values ± SD (n), where (n)- denotes number of analysis. ⁎ 5 L of water initial sample volume (MDA = 0.01 Bq/L).

Please cite this article as: Walencik-Łata, A., et al., The detailed analysis of natural radionuclides dissolved in spa waters of the Kłodzko Valley, Sudety Mountains, Poland, Sci Total Environ (2016), http://dx.doi.org/10.1016/j.scitotenv.2016.06.192

6

Spa

Polanica-Zdrój

Brand name of intake

238

U [mBq/L]

234

U [mBq/L]

U [μg/L]

234

U/238U

P-300

24.09.01

7.6 ± 0.7

20.7 ± 1.3

0.61 ± 0.05

2.7 ± 0.3

P-300a

18.07.07

6.7 ± 0.6

16.4 ± 1.0

0.55 ± 0.05

2.4 ± 0.3

12.07.13

6.0 ± 0.6

16.7 ± 1.1

0.48 ± 0.05

2.8 ± 0.3

Average

6.4 ± 0.4

16.6 ± 0.2

0.51 ± 0.03

2.6 ± 0.2

24.09.01

7.5 ± 0.6

16.9 ± 1.1

0.61 ± 0.05

2.2 ± 0.2

18.07.07

3.3 ± 0.4

8.7 ± 0.6

0.27 ± 0.03

2.6 ± 0.3

Average

5±2

13 ± 4

0.44 ± 0.17

2.4 ± 0.2

14.02.03

3.5 ± 0.4

7.5 ± 0.6

0.28 ± 0.03

2.2 ± 0.3

18.07.07

4.0 ± 0.5

7.3 ± 0.7

0.32 ± 0.04

1.8 ± 0.3

12.07.13

4.3 ± 0.7

8.9 ± 1.0

0.35 ± 0.06

2.1 ± 0.4

Average

3.9 ± 0.2

7.9 ± 0.5

0.32 ± 0.02

2.0 ± 0.1

14.02.03

5.7 ± 0.6

11.5 ± 1.0

0.46 ± 0.05

2.0 ± 0.3

18.07.07

7.3 ± 0.6

12.7 ± 0.9

0.59 ± 0.05

1.8 ± 0.2

12.07.13

8.1 ± 1.2

15.2 ± 1.8

0.66 ± 0.10

1.9 ± 0.4

Average

7.0 ± 0.7

13.1 ± 1.1

0.57 ± 0.06

1.9 ± 0.1

14.02.03

5.8 ± 0.7

12.0 ± 1.1

0.47 ± 0.06

2.1 ± 0.3

18.07.07

4.2 ± 0.4

10.2 ± 0.7

0.34 ± 0.03

2.4 ± 0.3

12.07.13

4.1 ± 0.7

8.3 ± 1.0

0.33 ± 0.05

2.1 ± 0.4

Average

4.7 ± 0.6

10.2 ± 1.1

0.38 ± 0.05

2.2 ± 0.1

17.07.07

19 ± 2.0

45 ± 4

1.5 ± 0.2

2.4 ± 0.3

25.09.01

15 ± 1

38 ± 2

1.23 ± 0.09

2.5 ± 0.2

12.07.13

16.4 ± 1.5

42 ± 3

1.3 ± 1.1

2.6 ± 0.3

Józef Stary

Pieniawa Józefa I

Pieniawa Józefa II

Wielka Pieniawa

Duszniki-Zdrój

Date of collection

Jan Kazimierz

226

Ra/238U

222

Rn/238U

222

Rn/226Ra

226

Ra/228Ra

Effective radiation dose [μSv/year] U + Ra

222

133 ± 17

660 ± 237

5.0 ± 1.8

16 ± 4

60

3

167 ± 11

2170 ± 170

13 ± 0.7

7±1

75

9

32 ± 13

4158 ± 1714

131 ± 19

2.2 ± 1.7

19

14

46 ± 4

4632 ± 516

101 ± 10

3.7 ± 1.4

15

12

17 ± 2

2979 ± 356

173 ± 12

3.4 ± 1.3

11

13

58 ± 9

3821 ± 544

66 ± 6

7.0 ± 2.4

19

11

Average

16.8 ± 1.1

42 ± 2

1.4 ± 0.1

2.5 ± 0.05

60 ± 6

1039 ± 73

5.0 ± 1.8

9.6 ± 0.8

65

11

B-1

25.09.01

13 ± 1

23 ± 2

1.09 ± 0.09

1.7 ± 0.2

22 ± 15

1215 ± 380

55 ± 43

1.6 ± 1.2

38

10

B-2 (Agata)

25.09.01

32 ± 3

100 ± 7

2.6 ± 0.2

3.1 ± 0.3

2.0 ± 1.0

1697 ± 232

838 ± 309

2.5 ± 4.1

7.8

35

B-3 (Jacek)

17.07.07

81 ± 4

239 ± 11

6.6 ± 0.3

2.9 ± 0.2

25.09.01

72 ± 5

215 ± 14

5.8 ± 0.4

3.0 ± 0.3

12.07.13

81 ± 5

234 ± 13

6.6 ± 0.4

2.9 ± 0.2

Average

78 ± 3

229 ± 7

6.3 ± 0.3

2.9 ± 0.03

9.0 ± 0.7

1138 ± 49

126 ± 3

3.0 ± 0.8

68

57

17.07.07

8.3 ± 1.2

25 ± 3

0.66 ± 0.09

3.0 ± 0.5

25.09.01

8.2 ± 0.8

25 ± 2

0.66 ± 0.06

3.1 ± 0.4

12.07.13

8.8 ± 1.0

29 ± 2

0.71 ± 0.08

3.3 ± 0.4

Average

8.4 ± 0.2

26.1 ± 1.3

0.68 ± 0.02

3.1 ± 0.1

115 ± 19

635 ± 121

5.5 ± 1.2

3.0 ± 0.7

91

3

17.07.07

1.5 ± 0.3

3.0 ± 0.4

0.12 ± 0.02

2.1 ± 0.5

25.09.01

1.1 ± 0.2

2.5 ± 0.3

0.09 ± 0.02

2.2 ± 0.5

B-4

Pieniawa Chopina

Rn

A. Walencik-Łata et al. / Science of the Total Environment xxx (2016) xxx–xxx

Please cite this article as: Walencik-Łata, A., et al., The detailed analysis of natural radionuclides dissolved in spa waters of the Kłodzko Valley, Sudety Mountains, Poland, Sci Total Environ (2016), http://dx.doi.org/10.1016/j.scitotenv.2016.06.192

Table 3 Activity concentrations of 238,234U in [mBq/L], uranium content in [μg/L], calculated effective doses in [μSv/year] (assuming 0.5 L daily consumption) and isotopic ratios in investigated waters.

1.4 ± 0.3

3.0 ± 0.4

0.11 ± 0.02

2.2 ± 0.6

Average

1.3 ± 0.1

2.8 ± 0.2

0.11 ± 0.01

2.1 ± 0.04

17.07.07

4.3 ± 0.4

10.7 ± 0.7

0.35 ± 0.03

2.5 ± 0.3

25.09.01

4.0 ± 0.4

9.7 ± 0.6

0.32 ± 0.03

2.4 ± 0.3

12.07.13

3.4 ± 0.4

10.4 ± 0.4

0.28 ± 0.03

3.1 ± 0.4

Average

3.9 ± 0.3

10.3 ± 0.3

0.32 ± 0.04

409 ± 77

6906 ± 1166

17 ± 3

1.9 ± 0.4

63

6

2.7 ± 0.2

144 ± 17

2593 ± 277

18 ± 2

2.7 ± 0.8

55

6

Zimny Zdrój

25.09.01

3.9 ± 0.4

6.0 ± 0.5

0.32 ± 0.03

1.5 ± 0.2

42 ± 21

13,891 ± 1446

330 ± 85

2.9 ± 4.2

16

35

Szczawina

Studzienne

23.10.07

1.0 ± 0.2

2.1 ± 0.3

0.08 ± 0.02

2.1 ± 0.5

91 ± 19

115,327 ± 24,593

1272 ± 57

1.3 ± 0.2

14

75

Długopole-Zdrój

Emilia

23.10.07

b0.5

0.8 ± 0.2

−

−

11.07.13

b0.5

1.0 ± 0.4

−

− −

−

1062 ± 164

3.2 ± 1.4

8.5

64

177 ± 83

129,486 ± 46,520

731 ± 90

1.0 ± 0.4

17

45

249 ± 145

165,278 ± 100,364

664 ± 125

2.6 ± 0.8

12

50

Renata

Kazimierz

Kudowa-Zdrój

K-200

−

0.9 ± 0.1

−

−

0.5 ± 0.2

0.7 ± 0.3

0.04 ± 0.02

1.3 ± 0.7

11.07.13

b0.5

b0.5

−

−

23.10.07

0.5 ± 0.3

1.2 ± 0.4

0.04 ± 0.02

2.6 ± 1.7

11.07.13

b0.5

b0.5

−

−

17.07.07

18 ± 2

53 ± 5

1.5 ± 0.2

2.9 ± 0.4

12.07.13

22 ± 2

75 ± 5

1.83 ± 0.16

3.3 ± 0.4

Average

20 ± 2

64 ± 11

1.65 ± 0.18

3.1 ± 0.2

32 ± 8

397 ± 66

13 ± 2

5.5 ± 2.8

48

5

No. 2 Moniuszko

12.07.13

1.5 ± 0.3

1.9 ± 0.3

0.12 ± 0.02

1.3 ± 0.3

78 ± 24

3917 ± 896

50 ± 8

1.0 ± 0.3

20

4

No. 3, Nowy Marchlewski

17.07.07

4.8 ± 0.6

8.2 ± 0.8

0.39 ± 0.05

1.7 ± 0.3

12.07.13

1.2 ± 0.4

2.2 ± 0.5

0.09 ± 0.03

1.9 ± 0.7

Average

3.0 ± 1.8

5.2 ± 3.0

0.24 ± 0.15

1.8 ± 0.1

23 ± 15

21,853 ± 13,402

937 ± 73

0.9 ± 0.2

14

42

17.07.07

1.4 ± 0.3

2.6 ± 0.4

0.11 ± 0.02

1.9 ± 0.4

12.07.13

2.9 ± 0.4

5.7 ± 0.6

0.24 ± 0.03

2.0 ± 0.3

Average

2.1 ± 0.8

4.2 ± 1.5

0.17 ± 0.06

1.93 ± 0.02

96 ± 53

8017 ± 2894

83 ± 20

2.9 ± 2.1

19

11

17.07.07

4.9 ± 0.6

7.8 ± 0.8

0.40 ± 0.05

1.6 ± 0.2

12.07.13

2.2 ± 0.4

3.6 ± 0.5

0.18 ± 0.03

1.6 ± 0.3

Average

3.5 ± 1.4

5.7 ± 2.1

0.29 ± 0.11

1.61 ± 0.02

57 ± 34

5498 ± 2199

96 ± 31

3.8 ± 1.8

17

12

17.07.07

33 ± 2

158 ± 7

2.7 ± 0.1

4.7 ± 0.3

12.07.13

31 ± 3

154 ± 10

2.5 ± 0.2

4.9 ± 0.5

Average

32 ± 1

156 ± 2

2.6 ± 0.1

4.8 ± 0.1

17.07.07

1.1 ± 0.2

2.6 ± 0.3

0.09 ± 0.02

2.3 ± 0.6

12 ± 4 39 ± 19

2942 ± 685 23,100 ± 10,612

252 ± 90 587 ± 350

− 3.5 ± 1.8

21 4.0

61 17

1.7 ± 0.8

3458 ± 1206

1981 ± 948

−

1.2

22

Śniadecki

Górne

Jeleniów

Average 23.10.07

J-150

Sarenka No. 2

No. 5

No. 6

17.07.07

11.9 ± 0.8

26.0 ± 1.4

0.97 ± 0.06

2.2 ± 0.2

12.07.13

8.1 ± 1.0

18 ± 2

0.66 ± 0.08

2.2 ± 0.3

Average

10 ± 2

22 ± 4

0.81 ± 0.16

2.2 ± 0.03

17.07.07

14 ± 2

25 ± 3

1.1 ± 0.1

1.8 ± 0.3

12.07.13

4.7 ± 0.7

8.6 ± 1.1

0.38 ± 0.06

1.8 ± 0.4

Average

9.2 ± 4.5

17 ± 8

0.75 ± 0.37

1.81 ± 0.01

2.1 ± 1.4

4193 ± 2390

2040 ± 1004

−

1.2

25

12.07.13

12.1 ± 1.3

31.1 ± 2.5

0.98 ± 0.10

2.6 ± 0.3

3.6 ± 1.2

6880 ± 1733

1901 ± 625

−

2.6

53 7

(continued on next page)

A. Walencik-Łata et al. / Science of the Total Environment xxx (2016) xxx–xxx

Please cite this article as: Walencik-Łata, A., et al., The detailed analysis of natural radionuclides dissolved in spa waters of the Kłodzko Valley, Sudety Mountains, Poland, Sci Total Environ (2016), http://dx.doi.org/10.1016/j.scitotenv.2016.06.192

No. 39

12.07.13

8

Spa

Lądek-Zdrój

Brand name of intake

Date of collection

238

U [mBq/L]

234

U [mBq/L]

U [μg/L]

234

U/238U

No. 7

12.07.13

3.1 ± 0.6

4.9 ± 0.8

0.25 ± 0.05

1.6 ± 0.4

Chrobry

28.03.2003

b0.5

b0.5

−

−

23.10.2007

b0.5

0.6 ± 0.3

−

−

11.07.2013

b0.5

b0.5

−

−

23.10.2007

0.7 ± 0.2

1.1 ± 0.3

0.06 ± 0.02

1.5 ± 0.6

11.07.2013

0.5 ± 0.3

3.2 ± 0.6

0.04 ± 0.02

6.8 ± 3.9

Average

0.6 ± 0.1

2.1 ± 1.0

0.05 ± 0.01

4.1 ± 2.6

28.03.2003

6.4 ± 0.4

18 ± 1

0.52 ± 0.04

2.8 ± 0.2

23.10.2007

14.5 ± 0.9

43 ± 2

1.17 ± 0.07

2.9 ± 0.2

11.07.2013

14.1 ± 1.4

42 ± 4

1.14 ± 0.11

3.0 ± 0.4

Dąbrówka

Jerzy

Average

11.7 ± 0.3

34 ± 8

0.94 ± 0.21

2.9 ± 0.1

L-2 (Zdzisław)

23.10.2007

b0.5

b0.5

−

−

11.07.2013

b0.5

b0.5

−

−

Skłodowska-Curie

23.10.2007

2.8 ± 0.4

6.7 ± 0.6

0.23 ± 0.03

2.4 ± 0.4 2.7 ± 0.7

Wojciech

11.07.2013

2.9 ± 0.6

7.8 ± 1.1

0.24 ± 0.05

Average

2.9 ± 0.1

7.3 ± 0.6

0.23 ± 0.01

2.5 ± 0.2

23.10.2007

8.8 ± 0.5

15.7 ± 0.8

0.71 ± 0.04

1.8 ± 0.1

11.07.2013

8.0 ± 0.9

12.1 ± 1.2

0.65 ± 0.07

1.5 ± 0.2

Average

8.4 ± 0.4

13.9 ± 1.8

0.68 ± 0.03

1.6 ± 0.1

Average-denotes arithmetic mean ± standard deviation of mean.

226

Ra/238U

222

Rn/238U

222

Rn/226Ra

226

Ra/228Ra

Effective radiation dose [μSv/year] U + Ra

222

Rn

17 ± 13

23,576 ± 11,914

1377 ± 1330

2.1 ± 1.5

5.9

47

−

−

13,091 ± 3571

−

0.5

84

19 ± 11

231,778 ± 48,476

12,355 ± 4414

−

0.6

87

7.7 ± 1.7

100,434 ± 23,848

13,129 ± 985

−

5.0

748

−

−

9064 ± 919

1.0 ± 0.4

2.3

77

9.3 ± 0.4

113,718 ± 8139

12,177 ± 812

−

1.5

208

1.4 ± 0.1

25,792 ± 1450

18,681 ± 781

−

0.8

138

A. Walencik-Łata et al. / Science of the Total Environment xxx (2016) xxx–xxx

Please cite this article as: Walencik-Łata, A., et al., The detailed analysis of natural radionuclides dissolved in spa waters of the Kłodzko Valley, Sudety Mountains, Poland, Sci Total Environ (2016), http://dx.doi.org/10.1016/j.scitotenv.2016.06.192

Table 3 (continued)

A. Walencik-Łata et al. / Science of the Total Environment xxx (2016) xxx–xxx

Fig. 2a) shows the relationship between uranium content and uranium activity ratio 234U/238U in the studied waters. Most waters exhibited uranium content lower than 0.5 μg/L (median = 0.47 μg/L) and uranium activity ratio 234U/238U between 2 and 3 (median = 2.3). Larger variations in uranium 234U/238U activity ratios were observed in waters with uranium content lower than 1 μg/L (Fig. 2a)). A correlation coefficient between 234U/238U activity ratio and U content is equal to r = 0.51, that is, the decay of 238U to 234U plays a less important role than the chemical dissolution of uranium in groundwaters (Fig. 2b)). The Pearson correlation coefficient equal to r = 0.51 indicates an average positive correlation. In oxidation conditions, the chemistry of water and the time of water – rocks contact occupy an essential role rather than fractionation processes. According to Osmond and Cowart (2000), water being in oxidation conditions is characterized by 234 U/238U activity ratio from 1 to 4 and uranium content from 0.1 μg/L to 1 μg/L. This fact was confirmed in the present studies. Fig. 2c) presents statistical analyses of mean values of 222Rn, total radium (226Ra + 228Ra) and total uranium (234U + 238 U) activity concentrations. The values of the median, the first (25%) and third (75%) quartile are shown on box-graphs. The presence of outliers demonstrates the log-normal distribution of the results. Also, the comparison of the mean and median values proves the lack of normal distribution. For instance, for 222Rn, the mean value of all results (N = 35) is equal to 94 Bq/L, while median 39 Bq/L shows a significant difference between the values of the outliers and the rest of the results. For a wide range of radioactivity content covering a few orders of magnitudes, the log-normal distributions describe the most environmental data. A correlation between activity concentrations of 234U and 238U isotopes (r = 0.97, N = 32) was observed. Also, a high positive correlation

9

(r = 0.63, N = 26) between concentration of 226Ra and 228Ra isotopes was noticed. There is no significant dependence between activity concentrations of 222Rn and 226Ra dissolved in the waters. Both low and high concentrations of 222Rn isotope in the investigated waters were observed, while 226 Ra concentrations were always low. On the other hand, lower concentrations of 222Rn dissolved in the waters were observed when the concentrations of 226Ra isotope were slightly higher (low negative correlation r = − 0.23, Fig. 3a)). In general, this may be explained by the fact that higher concentration of 222Rn is usually present in shallow circulation water characterized by low mineralization. In contrast, activity concentration of 222Rn decreases in highly mineralized water of deep circulation where simultaneously the concentration of 226Ra rises. The presence of radon in water is determined by α decay of 226 Ra isotope incorporated in the structure of minerals, or located on the surface of reservoir rocks. Moreover, the investigated waters are mainly situated close to faults where brittle deformations i.e. cracks and fissures enhance these waters in 222Rn (zones of the increased emanation coefficient), while the significant impact of radon produced from disintegration of 226Ra2 + ions dissolved in groundwater may only be observed in highly mineralized waters rich in dissolved 226Ra isotope. As a rule, there is no evident dependence (Fig. 3b)) between activity concentrations of 226Ra and 238U dissolved in water. The presence of radium in water is determined by direct recoil across the liquid – solid phase, where radium located on the surfaces of faults and cracks of reservoir rocks is washed out from cracks in reservoir rocks where it penetrates as a result of earlier nuclear decays, especially α – decay, in radioactive series. Then, it may be dissolved and adsorbed in the cracks

Fig. 2. The relation between: a) uranium content and 234U/238U activity ratios, b) 234U/238U activity ratios and uranium concentrations (234U + 238 U), c) the box plots for 222Rn, Ratot, Utot concentrations in investigated water intakes from the Kłodzko Land.

Please cite this article as: Walencik-Łata, A., et al., The detailed analysis of natural radionuclides dissolved in spa waters of the Kłodzko Valley, Sudety Mountains, Poland, Sci Total Environ (2016), http://dx.doi.org/10.1016/j.scitotenv.2016.06.192

10

A. Walencik-Łata et al. / Science of the Total Environment xxx (2016) xxx–xxx

Fig. 3. Dependences between: a) 222Rn-226Ra, b) 226Ra-238U, c) 222Rn-Utot, d) 226,228Ra – TDS, e) 238,234U-TDS, f) 222Rn-TDS.

several times, depending on the pH value and Eh potential conditions found on the border of groundwater/reservoir rock where groundwater flows and from where it is released. The obtained results clearly indicate that radium is more easily leached than 238U, since the latter is incorporated into structures of minerals of reservoir rocks. The presence of radium in water is determined by the direct recoil across the liquid – solid boundary during its formation, by solution of solids, by the radioactive decay of a parent isotope in solids, and by the desorption (Ruberu et al., 2005). Clearly, uranium has two natural valence states +IV and +VI, and it is mobile under oxidizing conditions but immobile under reducing conditions. Moreover, the mobility of uranium and its content in waters depends also on various parameters such as: pH, oxidation potential, mineral dissolution, partial pressure of CO2, reservoir rocks composition, ground-water flow and flow-path length (Paces et al., 2002). The geochemistry of uranium was already discussed in the literature (Osmond and Cowart, 1976; Osmond and Cowart, 2000; Hem, 1985; Regenspurg et al., 2009; Skeppström and Olofsson, 2007). Besides, there is a notable lack of 222Rn and 238U correlation (r = 0.03, N = 32) in the studied underground water (Fig. 3c)). This clearly indicates that 222Rn activity

concentrations have no connection with the Eh-pH of water which determines the level of uranium dissolved in it. The concentration of radon is also independent of the radioactive decays of 238U nuclei. Therefore, this fact proves the dominant role of diffusion process or the direct recoil of radon atoms from the grains of reservoir rocks as the source of gaseous 222 Rn dissolved in groundwater. Figs. 3d)–3e) present the correlations between activity concentrations for different isotopes and the mineralization of waters (TDS). The radium isotopes are leached from reservoir rocks proportionally to the other mineral agents. A high positive correlation (r = 0.57) was observed between activity concentrations of 226Ra and TDS values (Fig. 3d)), and there was a medium positive correlation (r = 0.43) between 228Ra activity concentration and TDS (Fig. 3d)). On the other hand, 234,238U activity concentrations were not correlated with TDS values (Fig. 3e)). The authors observed a moderate negative correlation between 222Rn activity concentration and mineralization of waters (r = −0.41, Fig. 3f)). Thus, this can be taken as an indication that higher 222 Rn activity concentrations were more likely to be observed in low mineralized waters of shallow circulation. This fact is indeed connected

Please cite this article as: Walencik-Łata, A., et al., The detailed analysis of natural radionuclides dissolved in spa waters of the Kłodzko Valley, Sudety Mountains, Poland, Sci Total Environ (2016), http://dx.doi.org/10.1016/j.scitotenv.2016.06.192

A. Walencik-Łata et al. / Science of the Total Environment xxx (2016) xxx–xxx

11

Fig. 4. Dependences between: a) concentration of 222Rn and depth of water intakes, b) concentration of 222Rn and depth of shallow circulation waters, c) TDS and depth of water intakes, d) TDS and depth of shallow circulation waters for acidulous waters.

with the increased emanation coefficient from the weathered reservoir rocks. In brief, the obtained results confirmed the previous investigations in this field (Przylibski, 2005, 2011). Furthermore, the obtained results indicate that mainly the chemical properties of radium and uranium isotopes affect their content and dissolution in water, not the radioactive decay of the already dissolved radionuclides. Radium is soluble in oxygen – poor groundwaters of deeper circulation and higher mineralization, whereas uranium is soluble in oxygen – rich conditions. The plots on Fig. 4 show that the 222Rn concentration decreases with the depth of the intakes. The highest values of radon activity concentrations were observed for the boreholes not deeper than 100 m b.g.l. This is clearly a result of the decrease of the emanation coefficient of reservoir rocks along with the increase of the depth of the intakes and the decrease of rock porosity with the depth of their layers. Indeed, a similar conclusion was presented by Przylibski (2005, 2011) in his publications concerning the underground water from the Polish part of the Sudety Mts. The correlation coefficient between 222 Rn concentrations and depths of the intakes leads to a moderate negative correlation (r = −0.39, Fig. 5a)). Moreover, as regards the depth of the circulation of shallow infiltration water, at the same depth equal to 30 m b.g.l, the activity concentration of 222Rn isotope varies within the range from 5 ± 1 Bq/L to 117 ± 5 Bq/L (Fig. 4b)). Analyzing the dependence between the depth of the intakes and the total dissolved solids, it can be concluded that deep circulating waters are characterized by higher TDS values (Fig. 4c), 4d)). The authors also observed a very high positive correlation (r = 0.72, Fig. 5c)) between the radium activity concentrations (226Ra + 228Ra) and the depth of the intakes. This may indicate that the chemical content of acidulous water including its TDS and the presence of radium isotopes is present at higher depths due to a longer water-reservoir rocks interaction time than that of shallow circulation water. Both the TDS and Ra activity content values rise with the depth and correlate (see Figs. 4 and 5). On the other hand, uranium activity concentrations (234U + 238U), depths of

analyzed intakes (Fig. 5e)) and depths of shallow infiltration water (up to 100 m b.g.l, Fig. 5f)) do not correlate (r = 0.26 and r = −0.07, respectively). Fig. 5e) and g) present the dependence of Utot or 234 U/238U and the depth of the intakes. One can see the rise of Utot or 234 U/238U together with the ingrowth of acidulous water intake, while the values of both analyzed parameters slightly diminished with the depth of the intake in shallow infiltration water (Fig. 5f)). Hence, the aforementioned facts may be interpreted as follows: in shallow water, the amount of dissolved oxygen decreases with the depth, so as Eh value. This leads to an observed, although small, decrease in Utot content. On the contrary, in carbonated water, due to a longer time of water contact with reservoir rocks, TDS values rise with the increase of the depth of water circulation. This fact causes the dissolution of larger amounts of both analyzed uranium isotopes. The underground water rich in CO2 of the studied region of the Kłodzka Valley is most often collected in several intakes in each town or site. The chemical types of detracted waters in most of the analyzed intakes from one region are identical, whereas TDS values are different. Moreover, the same chemical type of water along with the different TDS value may imply the dissolution of highly mineralized water of deep circulation by low mineralized water of shallow circulation (Ciężkowski, 1990). 3.2. Activity ratios On the basis of evaluated activity concentrations of uranium, radium and radon isotopes the isotope activity ratios 234U/238U, 226Ra/238U, 222 Rn/238U were calculated (Table 3). In 238U decay series 234U isotope is present. In closed geological systems older than 106 y, these isotopes should be in secular equilibrium (Osmond and Cowart, 1976). On the other hand, an open system exposed to weathering conditions and the circulation of groundwater may be the reason for the radioactive disequilibrium between these two isotopes. The processes responsible for that were extensively discussed in the literature (Osmond and Cowart, 1976, 2000; Suksi,

Please cite this article as: Walencik-Łata, A., et al., The detailed analysis of natural radionuclides dissolved in spa waters of the Kłodzko Valley, Sudety Mountains, Poland, Sci Total Environ (2016), http://dx.doi.org/10.1016/j.scitotenv.2016.06.192

12

A. Walencik-Łata et al. / Science of the Total Environment xxx (2016) xxx–xxx

Fig. 5. Dependences between: a) 222Rn – depth of water intakes, b) 222Rn – depth of shallow circulation waters, c) Ratot(226Ra + 228Ra) – depth of water intakes, d) Ratot(226Ra + 228Ra) – depth of shallow circulation waters for acidulous waters, e) Utot(238U + 234U) – depth of water intakes, f) Utot(238U + 234U) – depth of shallow circulation waters, g) 234U/238U – depth of water intakes for acidulous waters.

2001). The isotopic ratio of 234U/238U in the investigated groundwaters varies from 1.3 ± 0.7 to 6.8 ± 3.9 (Table 3), thus meaning that there is a disequilibrium between 238U and its daughter 234U, so the latter is more easily leached from a solid matrix to water than 238U. This is due to the increased vulnerability of 234U isotope to water resulting from the oxidation of uranium from the valence state IV + to VI +. Therefore, the most probable scenario for it is that after the decay, recoiling 234Th

atoms push lighter oxygen atoms in front of it, enriching the final position in oxidation spaces responsible for the 234U oxidation process (Suksi, 2001; Porceli, 2008 and publications herein). The values of the activity ratios: 226Ra/238U, 222Rn/238U varied in a range from 1.4 ± 0.1 to 409 ± 77 and from 397 ± 66 to 231,778 ± 48,476, respectively (Table 3). The obtained results indicate that 226Ra and 222Rn isotopes are better transported by groundwater than 238U

Please cite this article as: Walencik-Łata, A., et al., The detailed analysis of natural radionuclides dissolved in spa waters of the Kłodzko Valley, Sudety Mountains, Poland, Sci Total Environ (2016), http://dx.doi.org/10.1016/j.scitotenv.2016.06.192

Spa

Name of the water intake

Effective dose [μSv/year] gb1 238

U

g:1–2 234

U

Ra

Polanica-Zdrój

P-300 P-300a Pieniawa Józefa I Pieniawa Józefa II W. Pieniawa

0.47 0.39 0.24 0.43 0.29

865 909 154 104 233

Duszniki- Zdrój

B-3 (Jacek) Pieniawa Chopina

4.9 15.5 607 0.08 0.19 466

Szczawina

Studzienne

0.06 0.14

Długopole-Zdrój

Emilia Renata Kazimierz

Kudowa-Zdój

K-200 No. 2 (Moniuszko) No. 3 (Nowy Marchlewski)

Jeleniów

Lądek-Zdrój

228

Ra U+Ra

U

226

Ra

228

Ra U+Ra

g:7–12

238

U

234

0.3 0.3 0.1 0.2 0.2

0.11 0.09 0.06 0.10 0.07

1287 1914 1551 2018

1.7 5.4 124 0.03 0.07 95

244 295

376 390

79

383

462

0.02 0.05

16

73

– 0.06 81 0.03 0.05 83 0.03 0.08 102

162 513 254

242 596 356

– 0.02 0.01 0.02 0.01 0.03

17 17 21

31 97 48

1.3 4.3 552 0.09 0.13 97 0.19 0.35 60

641 606 438

1198 704 499

0.45 1.51 113 0.03 0.04 20 0.07 0.12 12

J-150 No. 2 No. 5 No. 6 No. 7

2.0 0.62 0.57 0.75 0.19

10.5 323 1.49 15 1.13 16 2.10 37 0.33 45

– – – – 137

336 17 18 40 183

0.71 0.22 0.20 0.26 0.07

3.70 0.52 0.40 0.74 0.12

Chrobry Dąbrówka Jerzy L-2 (Zdzisław) Skłodowska-Curie

– 0.04 0.72 – 0.18

0.04 0.14 2.31 – 0.49

– – – 71 –

9 10 80 83 24

– 0.01 0.26 – 0.06

34

37

12

3000 –

0.17 0.14 0.09 0.15 0.10

g:2–7 234

245 353 82 59 88

470

1223 1787 419 302 447

U

68 166 50 37 41

9 9 77 11 23

356 876 264 197 214

238

0.49 177 0.39 186 0.19 31 0.31 21 0.24 48

Dose conversion factor (∙10−8) [Sv/Bq]

1.4 1.1 0.53 0.89 0.69

226

U

226

Ra

228

Ra U+Ra

238

U

g:12–17

234

U

226

Ra

228

Ra U+Ra

238

234

U

gN17 (2 l consumption/day) U

226

Ra

228

Ra U+Ra

238

U

114 120 20 14 31

40 99 30 22 24

155 220 50 36 55

0.09 0.08 0.05 0.09 0.06

0.28 147 0.22 155 0.11 26 0.18 18 0.14 40

46 114 34 26 28

194 269 61 44 68

0.09 0.08 0.05 0.09 0.06

0.28 276 0.22 290 0.11 49 0.18 33 0.14 74

63 155 47 35 38

339 445 96 68 112

0.25 0.21 0.13 0.23 0.15

1.14 3.7 0.02 0.05

80 61

146 176

231 237

0.97 3.1 103 0.02 0.04 79

167 202

275 281

1.0 3.1 194 0.02 0.04 149

227 274

425 423

89

0.01 0.03

10

43

54

0.01 0.03

13

50

63

0.01 0.03

25

68

47 114 69

– 0.01 0.01 0.01 0.01 0.02

11 11 13

18 58 29

29 69 42

– 0.01 0.01 0.01 0.01 0.02

14 14 17

21 67 33

35 81 50

– 0.01 0.01 0.01 0.01 0.02

26 26 32

29 91 45

122 115 83

236 135 96

0.30 1.0 0.02 0.03 0.04 0.08

73 13 8

73 69 50

147 82 58

0.25 0.86 0.02 0.03 0.04 0.07

94 17 10

83 79 57

178 95 67

0.25 0.86 176 0.02 0.03 31 0.04 0.07 19

66 3 3 8 9

– – – – 26

70 4 4 9 35

0.47 0.15 0.13 0.18 0.05

2.5 0.35 0.27 0.50 0.08

43 2.0 2.1 4.9 6.0

– – – – 16

46 2.5 2.6 5.6 22

0.40 0.12 0.11 0.15 0.04

2.1 0.30 0.23 0.42 0.07

55 3 3 6 8

– – – – 18

58 3 3 7 26

0.40 0.12 0.11 0.15 0.04

0.01 0.05 0.81 – 0.17

2 2 16 2 5

– – – 14 –

2 2 17 16 5

– – 0.17 – 0.04

0.01 0.03 0.55 – 0.12

1.1 1.2 10 1.5 3.0

– – – 8.1 –

1.1 1.3 11 9.6 3.2

– 0.01 0.14 – 0.04

0.01 0.03 0.46 0.10

1.5 1.6 13 1.9 3.90

– – – 9.25 –

1.5 1.6 14 11 4.0

13

96

570

–

8.0

88

62

340

–

6.8

7.4

80

390

–

234

U

226

Ra

228

Ra U+Ra

33 81 24 18 20

240 298 61 44 76

2.6 8.2 145 0.04 0.10 111

118 143

274 254

93

0.03 0.08

19

35

54

54 117 77

– 0.03 0.02 0.03 0.02 0.04

19 20 24

15 47 23

34 67 48

113 107 77

290 138 97

0.67 2.27 131 0.05 0.07 23 0.10 0.19 14

59 56 40

193 79 55

2.1 103 0.30 5 0.23 5 0.42 12 0.07 15

– – – – 24

106 5 6 13 39

1.1 0.33 0.30 0.40 0.10

5.6 0.79 0.60 1.11 0.17

77 3.6 3.9 8.9 11

– – – – 13

84 4.7 4.8 10 24

– 0.01 0.14 – 0.03

0.01 0.03 0.46 – 0.10

– – – 12.57 –

2.7 3.0 25 16 7.4

– 0.02 0.38 – 0.09

0.02 0.08 1.22 – 0.26

2.0 2.2 18 2.7 5.5

– – – 6.5 –

2.1 2.3 20 9.3 5.8

6.7

7.4

530

–

4.5

4.9

28

69

–

2.7 3.0 24 3.6 7.3 150

0.74 206 0.59 217 0.28 37 0.47 25 0.36 55

A. Walencik-Łata et al. / Science of the Total Environment xxx (2016) xxx–xxx 13

Please cite this article as: Walencik-Łata, A., et al., The detailed analysis of natural radionuclides dissolved in spa waters of the Kłodzko Valley, Sudety Mountains, Poland, Sci Total Environ (2016), http://dx.doi.org/10.1016/j.scitotenv.2016.06.192

Table 4 Effective radiation doses in [μSv/year] for different human age groups due to uranium and radium consumption with drinking waters (bottled waters and available for free for local inhabitants, 0.5 L daily consumption excluding adults group (2 L). Dose conversion factors were taken from the Decree of the Polish Council of Ministers (2005) (Dz. U., No 20, poz. 168).

14

A. Walencik-Łata et al. / Science of the Total Environment xxx (2016) xxx–xxx

isotope. The isotopic 222Rn/226Ra activity ratio varies in a range from 5.0 ± 1.8 to 18,681 ± 781 (Table 3). It presumably means that almost the whole 222Rn dissolved in water originates from the gaseous 222Rn liberated from reservoir rocks to water. Only a very small part, comprising in some intakes maximum 20% of all atoms dissolved in groundwater, may arise due to the radioactive decay of the parent nuclide 226Ra2+ dissolved in this water. This is essentially in agreement with the results published earlier by Przylibski (2005, 2011). 226 Ra/228Ra activity ratio in the investigated groundwaters varied in a range from 0.9 ± 0.2 to 16 ± 4 with median 2.9. This may imply that reservoir rocks contain higher concentrations of 226Ra than 228Ra. On the other hand, preferential leaching or lixiviation from host rocks of 226 Ra isotope in comparison with 228Ra may be explained by their origin. Namely, each α recoil causes a lattice destruction and preferential mobilization of daughters. In uranium 238U series 226Ra isotope is generated after three consecutive α decays, in contrast to the isotope 228Ra which is produced by only one α decay of 232Th isotope. Hence, the lattice destruction after three α decays is larger than after one α decay and this causes preferential vulnerability of 226Ra leaching during water/ reservoir rock interaction. 3.3. Dose assessment This region of Poland is particularly rich in groundwater which is constantly consumed by people living there and tourists coming there on holiday. Assuming that mineral water constitutes only part of daily regular drinking water consumption, 0.5 L per day of mineral or spring water intake was assumed in dose estimation. The calculated effective radiation doses due to 226,228Ra and 238,234U intake with drinking water are presented in Table 3. The summed effective radiation doses were calculated on the basis of dose conversion factors equal to 2.8·10−7 Sv/Bq, 6.9·10−7 Sv/Bq, 4.9·10−8 Sv/Bq and 4.5·10−8 Sv/Bq for 226Ra, 228Ra 234U and 238U, respectively (WHO, 2011). The effective radiation doses for some of the waters of the Kłodzko Valley from 222 Rn ingestion were discussed previously (Kozłowska et al., 2010a), but these values were now completed in order to gather a full data base for all water intakes present in this region. In the present study, the authors extended the dose estimation by other toxic isotopes such as 226,228Ra and 238,234U. 222 Rn is a noble gas and part of it is removed during water usage. The doses were calculated assuming a consumption of 0.5 L of water per day from which radon is not removed according to the recommendation (OHJE DIRECTIV GUIDE, 1993). The effective doses from 222Rn ingestion were calculated on the basis of the dose conversion factor equal to 3.5 × 10− 9 Sv/Bq (National Research Council, 1999). The obtained values (Table 3) varied in a range from 3 μSv/year to 748 μSv/year. The summed effective doses from 226,228Ra and 234,238U consumption with drinking water varied from 0.5 μSv/year to 91 μSv/year. According to the decree of the Polish Ministry of Health (2015), WHO guidelines (WHO, 2011) as well as EU recommendations (Council Directive, 2013) on the requirements concerning the quality of drinking water, it was estimated that the summed annual effective dose from all radionuclides except for tritium, potassium and radon cannot exceed the value of 100 μSv/year. However, mineral waters are not explicitly taken into account in these regulations, since the use of this water as standard drinking water is not expected. The obtained results do not exceed the limit. Nonetheless, it is worth noting that only 0.5 L of water consumption was assumed for calculations. Most of these mineral waters are bottled and are commercially available throughout the country and abroad. Some of the waters are freely available to local inhabitants. The effective radiation dose for these waters was calculated for different human age groups (Table 4), assuming the consumption of 0.5 L of water per day and dose conversion factors taken from the Decree of the Polish Council of Ministers (2005). Bottled spring waters are often used to prepare meals and drinks for children and infants. However, most of the waters which

are bottled or are available for free are highly mineralized (Table 1) and are not recommended for infants, hence the dose values presented herein are only estimates. For adults (age group N 17 years), 2 L/day was used in dose calculations. To summarize, the calculated effective radiation doses (Table 4) for some waters are higher than the limit of intake. One can conclude on the basis of the obtained values that a significant impact on the received doses comes from radium isotopes. 4. Conclusions The measurements of natural radioactivity in the waters from selected spas of the Kłodzko Valley were performed. The presence of high radon (up to 1171 Bq/L) content in the investigated groundwaters is due to favorable geological conditions resulting from the presence of weathered rocks, faults and deep fissures with the increased emanation coefficient. The concentrations of radium isotopes (especially 226Ra) in the studied waters were considerably higher than those of uranium. The activity concentrations of both isotopes of uranium and of both isotopes of radium were well correlated to each other in the studied waters. This implies that the chemical properties of uranium and radium influence the concentration of these isotopes in water. The higher the TDS values and the deeper the groundwater circulation was, the higher radium content and the lower radon content were observed. On the other hand, there was no significant relation between TDS and uranium content. The investigated waters exhibited radioactive disequilibrium between isotopes belonging to the same radioactive chain and 226Ra and 222 Rn isotopes were better transported with water than 238U isotope. The concentrations of radium isotopes vary greatly despite close location of the particular waters and are independent of the concentrations of parent isotope 238U. The obtained results of 226Ra/228Ra activity ratio (median: 2.9) in the measured waters imply that reservoir rocks contain higher concentrations of 226Ra than 228Ra. The higher values of radium isotopes were observed at higher depths of intakes due to the longer water – reservoir rocks interaction time. The concentrations of radon and uranium diminished with depth of intakes. A dose assessment due to isotope consumption with drinking water was performed and the obtained values indicated that mainly radium isotopes contribute to the committed effective doses. Given the adult group and taking into account only 0.5 L daily consumption of water, the total effective doses from radium and uranium (excluding radon) do not exceed the limit of 100 μSv/year. However, if 2 L were to be assumed, which is highly probable due to the free availability of some waters, the limit of 100 μSv/year would be exceeded considerably, up to 298 μSv/year for the adult group. Moreover, taking into account the chemical toxicity of uranium, none of the investigated waters exceeded the limit set by WHO. Acknowledgments A.W.Ł acknowledges support from Polish Ministry of Science and Higher Education, project: N N305 101035. References Adamczyk-Lorenc, A., 2007. Hydrogeochemical background of radon in groundwaters of the Sudetes (Ph.D. Thesis) Wrocław University of Technology, Faculty of Geoengineering, Mining and Geology, Wrocław (Polish). Bareja, E., Sałdan, M., Strzelecki, R., 1987. Uranium and thorium ores. In: Osika, R. (Ed.), Geological Structure of Poland. Wydawnictwa Geologiczne, Warszawa (Polish). Bijwaard, H., Brugmans, M.J., Leenhouts, H.P., 2004. Two-mutation models for bone cancer due to radium, strontium and plutonium. Radiat. Res. 162, 171–184. Borucki, J., Głowacki, Z., Masłowski, W., Sałdan, M., Uberna, J., Zajączkowski, W., 1967. Estimation of Prospection Perspectives of Uranium Ore Deposits in Poland. Prace Instytutu Geologicznego, Wydawnictwa Geologiczne, Warszawa (Polish). Carnes, B.A., Groer, P.G., Kotek, T.J., 1997. Radium dial workers: issues concerning dose response and modeling. Radiat. Res. 147, 707–714. Chau, N.D., Dulinski, M., Jodłowski, P., Nowak, J., Różański, K., Sleziak, M., et al., 2011. Natural radioactivity in groundwater – a review. Isot. Environ. Health Stud. 47 (4), 415–437.

Please cite this article as: Walencik-Łata, A., et al., The detailed analysis of natural radionuclides dissolved in spa waters of the Kłodzko Valley, Sudety Mountains, Poland, Sci Total Environ (2016), http://dx.doi.org/10.1016/j.scitotenv.2016.06.192

A. Walencik-Łata et al. / Science of the Total Environment xxx (2016) xxx–xxx Chau, N.D., Rajchel, L., Nowak, J., Jodłowski, P., 2012. Radium isotopes in the Polish Outer Carpathian mineral waters of various chemical composition. J. Environ. Radioact. 112, 38–44. Ciężkowski, W., 1990. A study on the hydrogeochemistry of mineral and thermal waters in the Polish Sudety Mountains (SW Poland). Wrocław: Scientific Papers of the Institute of Geotechnics of the Technical University of Wrocław No. 60, Series Monographs No. 19 (Polish). Ciężkowski, W., Przylibski, T.A., 1997. Radon in waters from health resorts of the Sudety Mts. (SW Poland). Appl. Radiat. Isot. 48 (6), 855–856. Ciężkowski, W., Michniewicz, M., Przylibski, T.A., 2011. Thermal waters of Lower Silesia. In: Żelaźniewicz, A., Wojewoda, W., Ciężkowski, W. (Eds.), Mezozoik i kenozoik Dolnego Śląska. WIND, Wrocław, pp. 107–120 (Polish with English abstract). Council Directive, 2013. 2013/51/EURATOM of 22 October 2013 laying down requirements for the protection of the health of the general public with regard to radioactive substances in water intended for human consumption. OJ L 296, 12–21 7.11. Currie, L.A., 1968. Limits for qualitative detection and quantitative determination. Anal. Chem. 40 (3), 586–592. Darby, S., Hill, D., Doll, R., 2001. Radon: A likely carcinogen at all exposures. Ann. Oncol. 12, 1341–1351. Darby, S., Hill, D., Auvinen, A., Barros-Dios, J.M., Baysson, H., Bochicchio, F., et al., 2005. Radon in homes and risk of lung cancer: collaborative analysis of individual data from 13 European case-control studies. Br. Med. J. 330 (7485), 223–226. Darby, S., Hill, D., Deo, H., Auvinen, A., Barros-Dios, J.M., Baysson, H., et al., 2006. Residential radon and lung cancer – detailed results of a collaborative analysis of individual data on 7148 persons with lung cancer and 14,208 persons without lung cancer from 13 epidemiologic studies in Europe. Scand. J. Work Environ. Health 32 (Suppl. 1), 1–84. Decree of the Polish Council of Ministers, 2005. Dz. U. No 20 (poz. 168, 18.01.2005. Polish). Decree of the Polish Ministry of Health, 2015. Dz. U. 20 (poz. 1989, 13.11.2015. Polish). EPA (Environmental Protection Agency), 2000. National Primary Drinking Water Regulations. Radionuclides; Final Rule. 40 CFR Parts 9 pp. 141–142. Grosche, B., Kreuzer, M., Kreisheimer, M., Schnelzer, M., Tschense, A., 2006. Lung cancer risk among German male uranium miners: a cohort study, 1946–1998. Br. J. Cancer 95, 1280–1287. Haque, A.K.M.M., Kirk, A.E., 1992. Environmental radon and cancer risk. Radiat. Prot. Dosim. 45, 639–642. Hem, J.D., 1985. Study and interpretation of the chemical characteristics of natural water. U. S. Geol. Surv. Water Supply Pap. 2254. IARC, 1988. Man-made mineral fibres and radon. IARC Monographs on the Evaluation of Carcinogenic Risks to Humans 43. International Agency for Research on Cancer, World Health Organization, Lyon, France. IARC, 2001. Ionizing radiation. Some Internally Deposited RadionuclidesIARC Monographs on the Evaluation of Carcinogenic Risks to Humans Vol. 78, Part 2. International Agency for Research on Cancer, World Health Organization, Lyon, France. IARC, 2012. Radiation. A Review of Human CarcinogensIARC Monographs on the Evaluation of Carcinogenic Risks to Humans 100D. International Agency for Research on Cancer, World Health Organization, Lyon, France. Isajenko, K., Piotrowska, B., Fujak, M., Kardaś, M., 2012. Radiation Atlas of Poland. 2011. Central Laboratory for Radiological Protection, Biblioteka Monitoringu Środowiska, Warszawa. Karnkowski, P.H., 2008. Tectonic subdivision of Poland – Polish Lowlands. Prz. Geol. 56, 895–903 In Polish with English abstract. Kozłowska, B., 2009. Natural Radioactivity of Spring Waters in Spas of Southern Poland. Wydawnictwo Uniwersytetu Śląskiego, Katowice (Polish). Kozłowska, B., Hetman, A., Zipper, W., 1999. Determination of 222Rn in natural water samples from heath resorts in the Sudety Mountains by the liquid scintillation technique. Appl. Radiat. Isot. 51, 475–480. Kozłowska, B., Walencik, A., Dorda, J., Zipper, W., 2010a. Radon in groundwater and dose estimation for inhabitants in Spas of the Sudety Mountain area. Poland Applied Radiation and Isotopes 68, 854–857. Kozłowska, B., Walencik, A., Przylibski, T.A., Dorda, J., Zipper, W., 2010b. Uranium, radium and radon isotopes in selected brines of Poland. Nukleonika 55 (4), 519–522. Krewski, D., Lubin, J.H., Zielinski, J.M., Alavanja, M., Catalan, V.S., Field, R.W., et al., 2005. Residential radon and risk of lung cancer: a combined analysis of 7 North American case-control studies. Epidemiology 16, 137–145. Krewski, D., Lubin, J.H., Zielinski, J.M., Alavanja, M., Catalan, V.S., Field, R.W., et al., 2006. A combined analysis of North American case-control studies of residential radon and lung cancer. J. Toxicol. Environ. Health A 69, 533–597. Leenhouts, H.P., Brugmans, M.J., 2000. An analysis of bone and head sinus cancers in radium dial painters using a two-mutation carcinogenesis model. J. Radiol. Prot. 20, 169–188. Lubin, J.H., 2003. Studies of radon and lung cancer in North America and China. Radiat. Prot. Dosim. 104 (4), 315–319. Lubin, J.H., Wang, Z.Y., Boice Jr., J.D., Xu, Z.Y., Blot, W.J., Wang, L.D., et al., 2004. Risk of lung cancer and residential radon in China: pooled results of two studies. Int. J. Cancer 109, 132–137. Miecznik, J.B., Strzelecki, R., Wołkowicz, S., 2011. Uranium in Poland – history of prospecting and chances for finding new deposits. Prz. Geol. 59 (10), 688–697 In Polish with English abstract. National Research Council, 1999. Risk Assessment of Radon in Drinking Water. National Academy Press, Washington. Narkiewicz, M., Dadlez, R., 2008. Geological regional subdivision of Poland – general guidelines and proposed schemes of sub-Cenozoic and sub-Permian units. Prz. Geol. 56 (5), 391–397 (In Polish with English abstract).

15

Nekolla, E.A., Kreisheimer, M., Kellerer, A.M., Kuse-Isingschulte, M., Gössner, W., Spiess, H., 2000. Induction of malignant bone tumors in radium-224 patients: risk estimates based on the improved dosimetry. Radiat. Res. 153 (1), 93–103. Nowak, J., Chau, N.D., Rajchel, L., 2012. Natural radioactive nuclides in the thermal waters of the Polish Inner Carpathians. Geol. Carpath. 63 (4), 343–351. OHJE DIRECTIV GUIDE, 1993. Radioactivity of Household Water. Finnish Centre for Radiation and Nuclear Safety. Omulecki, A., Nowak, A., Zalewska, A., 1996. Spa theraphy in Poland. Clin. Dermatol. 14, 679–683. Osmond, J.K., Cowart, J.B., 2000. U-series nuclides as tracers in groundwater hydrology. In: Cook, P.G., Herczeg, A.L. (Eds.), Environmental Tracers in Subsurface Hydrogeology. Kluwer Academic Publishers, New York. Osmond, J.K., Cowart, J.B., 1976. The theory and uses of natural uranium isotopic variations in hydrology. At. Energy Rev. 14 (4), 621–679. Paces, J.B., Ludwig, K.R., Peterman, Z.E., Neymark, L.A., 2002. 234U/238U evidence for local recharge and patterns of groundwater flow in the vicinity of Yucca Mountain, Nevada, USA. Appl. Geochem. 17, 751–779. Plewa, M., Plewa, S., 1992. Petrophysics. Wydawnictwo Geologiczne, Warszawa (Polish). POLISH NORM, 1989. No: PN-89/ZN-70072. Radium Isotopes Determination in Water With LSC Method. Wydawnictwa Normalizacyjne “Alfa”, Warszawa (Polish). Porceli, D., 2008. Investigating groundwater processes using U- and Th-Series Nuclides. In: Krishnaswami, S., Cochran, J.K. (Eds.), U-Th Series Nuclides in Aquatic Systems, first ed. Radioactivity in the Environment 13. Elsevier. Przeniosło, S., 1970. The geochemistry of uranium in alluvia sediments of the eastern part of the metamorphic Lądek and Śnieżnik Kłodzki area. Z badań petrograficznomineralogicznych i geochemicznych w Polsce 224. Biuletyn Instytutu Geologicznego, Warszawa, pp. 205–298 T. IV. Przylibski, T.A., 2005. Radon. Specific Component of Medicinal Waters in the Sudety Mountains. Oficyna Wydawnicza Politechniki Wrocławskiej, Wrocław (Polish). Przylibski, T.A., 2011. Shallow circulation groundwater - the main type of water containing hazardous radon concentration. Nat. Hazards Earth Syst. Sci. 11, 1695–1703. Przylibski, T.A., Żebrowski, A., 1999. Origin of radon in medicinal waters of Lądek Zdrój (Sudety Mountains, SW Poland). J. Environ. Radioact. 46, 121–129. Przylibski, T.A., 2000a. Estimating the radon emanation coefficient from crystalline rocks into groundwater. Appl. Radiat. Isot. 53 (3), 473–479. Przylibski, T.A., 2000b. 222Rn concentration changes in medicinal groundwaters of Lądek Zdrój (Sudety Mountains, SW Poland). J. Environ. Radioact. 48 (3), 327–347. Przylibski, T.A., 2004. Concentration of 226Ra in rocks of the southern part of Lower Silesia (SW Poland). J. Environ. Radioact. 75 (2), 171–191. Przylibski, T.A., Dorda, J., Kozłowska, B., 2002. The occurence of 226Ra and 228Ra in groundwaters of the Polish Sudety Mountains. Nukleonika 47 (2), 59–64. Przylibski, T.A., Mamont-Cieśla, K., Kusyk, M., Dorda, J., Kozłowska, B., 2004. Radon concentrations in groundwaters of the Polish part of the Sudety Mountains (SW Poland). J. Environ. Radioact. 75 (2), 193–209. Przylibski, T.A., Gorecka, J., Kula, A., Fijałkowska-Lichwa, L., Zagożdżon, K., Zagożdżon, P., et al., 2014. 222Rn and 226Ra activity concentrations in groundwaters of southern Poland: new data and selected genetic relations. J. Radioanal. Nucl. Chem. 301 (3), 757–764. Regenspurg, S., Schid, D., Schäfer, T., Huber, F., Malmström, M.E., 2009. Removal of uranium(VI) from aqueous phase by iron(II) minerals in presence of bicarbonate. Appl. Geochem. 24, 1617–1625. Rowland, R.E., Stehney, A.F., Lucas Jr., HF, 1978. Dose-response relationships for female radium dial workers. Radiat. Res. 76, 368–383. Rowland, R.E., Stehney, A.F., Lucas, H.F., 1983. Dose-response relationships for radium-induced bone sarcomas. Health Phys. 44 (Supplement 1), 15–31. Ruberu, S.R., Liu, Y., Perera, S.K., 2005. Occurrence of 224Ra, 226Ra, 228Ra, gross alpha, and uranium in California groundwater. Health Phys. 89 (6). Sawicki, L. Geological Map of Lower Silesia Region (Without Quaternary Deposits). Scale 1:200,000. Warszawa: Instytut Geologiczny, Wydawnictwa Geologiczne; 1966. Polish. Sawicki, L. Geological Map of Lower Silesia Region With Adjacent Areas of Czech Republic and Germany (Without Quaternary Deposits). Scale 1:100,000. Warszawa: Państwowy Instytut Geologiczny; 1995. Polish. Sill, C.W., 1987. Precipitation of actinides as fluorides or hydroxides for high resolution alpha spectrometry. Nuclear Chem. Waste Mgmt. 7. Skeppström, K., Olofsson, B., 2007. Uranium and radon in groundwater. An overview of the problem. European Water 17/18, 51–62. Spiers, F.W., Lucas, H.F., Rundo, J., Anast, G.A., 1983. Leukaemia incidence in the U.S. dial workers. Health Phys. 44 (Supplement 1), 65–72. Stebbings, J.H., Lucas, H.F., Stehney, A.F., 1984. Mortality from cancers of major sites in female radium dial workers. Am. J. Ind. Med. 5 (6), 435–459. Suksi, J., 2001. Natural Uranium as a Tracer in Radionuclide Geosphere Transport Studies [Dissertation]. University of Helsinki, Finland. Suomela, J., 1993a. Method for determination of Radon-222 in water by liquid scintillation counting. ISO Norm: ISO/TC147/SC3/WG6. Suomela, J., 1993b. Method for determination of U-isotopes in water. Swedish Radiation Institute Document. Tomášek, L., Rogel, A., Tirmarche, M., Mitton, N., Laurie, D., 2008. Lung cancer in French and Czech uranium miners: radon-associated risk at low exposure rates and modifying effects of time since exposure and age at exposure. Radiat. Res. 169 (2), 125–137. Walencik, A., 2010. Uranium 234,238U Concentrations and 234U/238U Activity Ratios in Mineral, Medicinal and Bottled Waters in Selected Localities From Sudety and Carpathian Mountains (Ph.D. Thesis) Univ. of Silesia, Katowice (Polish).

Please cite this article as: Walencik-Łata, A., et al., The detailed analysis of natural radionuclides dissolved in spa waters of the Kłodzko Valley, Sudety Mountains, Poland, Sci Total Environ (2016), http://dx.doi.org/10.1016/j.scitotenv.2016.06.192

16

A. Walencik-Łata et al. / Science of the Total Environment xxx (2016) xxx–xxx

Walencik, A., Kozłowska, B., Dorda, J., Zipper, W., 2010. Natural radioactivity in underground water from the Outer Carpathians in Poland with the use of nuclear spectrometry techniques. Appl. Radiat. Isot. 68, 839–843. Walencik, A., Kozłowska, B., Dorda, J., Zipper, W., 2012. Long lived natural radioactive elements in spa waters of southern Poland – dose assessment and health hazard evaluation. Acta Phys. Pol. B 43 (2), 345–350. WHO, 2011. Guidelines for Drinking Water Quality. Chapter 9. fourth ed. Switzerland.

Wick, R.R., Nekolla, E.A., Gaubitz, M., Schulte, T.L., 2008. Increased risk of myeloid leukaemia in patients with ankylosing spondylitis following treatment with radium-224. Rheumatology 47, 855–859. http://dx.doi.org/10.1093/rheumatology/ken060. Znosko, J., 1998. Tectonic atlas of Poland. Warszawa, Polish Geological Institute. Zuber, A., Weise, S.M., Osenbrück, K., Grabczak, J., Ciężkowski, W., 1995. Age and recharge area of thermal waters in Lądek Spa (Sudeten, Poland) deduced from environmental isotope and noble gas data. J. Hydrol. 167, 327–349.

Please cite this article as: Walencik-Łata, A., et al., The detailed analysis of natural radionuclides dissolved in spa waters of the Kłodzko Valley, Sudety Mountains, Poland, Sci Total Environ (2016), http://dx.doi.org/10.1016/j.scitotenv.2016.06.192