Journal of Environmental Radioactivity 132 (2014) 21e30

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Journal of Environmental Radioactivity

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222 220
Rn, Rn and other dissolved gases in mineral waters of southeast
Brazil
Daniel Marcos Bonotto*
Departamento de Petrologia e Metalogenia, IGCE e Instituto de Geociências e Ciências Exatas, UNESP e Universidade Estadual Paulista Júlio de Mesquita
Filho, Av. 24-A, No. 1515 e CP 178, Bela Vista CP 178, CEP 13506-900 Rio Claro, SP, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: This paper describes the natural radioactivity due to 222Rn and 220Rn in mineral waters occurring at São
Received 20 September 2013 Paulo and Minas Gerais states, Brazil, that are extensively used for drinking in public places, bottling and
Received in revised form bathing purposes, among other. The measurements of these alpha-emitting radionuclides were also
8 January 2014
accompanied by the monitoring of temperature and some dissolved gases (O2, CO2 and H2S) in 75 water
Accepted 10 January 2014
Available online 14 February 2014
sources located in 14 municipalities of those states. Eight water sources yielded 220Rn activity concen-
tration values below the detection limit of 4 mBq/L. On other hand, 222Rn activity concentration values
exceeding the WHO guidance level of 100 Bq/L in drinking-water for public water supplies were found in
Keywords:
Radon and thoron
two springs, named Villela and Dona Beja, whose discharge occurs in areas characterized by the presence
Mineral waters of enhanced levels of natural radioelements in rocks. The obtained results were compared with the
Dissolved gases guidelines of the Brazilian Code of Mineral Waters (BCMW) that was established in 1945 and is still in
Radiation dose force in the country. The 222Rn and 220Rn activity concentration data allowed perform dose radiation
calculations based on the potential alpha energy concentration (PAEC), whose implications for health risk
have been also considered in this paper.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction In Brazil, the production and commercialization of mineral wa-

In many countries, spring waters have been extensively used for
consumption purposes as an option to tap water, as many people
believe they are healthy and/or can be utilized for health cures.
Additionally, economic reasons have also favored their use as
bottled waters so that the commercialization of mineral waters has
widely increased.
The thermal and mineral waters use in Brazil is not recent due to
arrival of European immigrants, mainly from Portugal. For instance,
Gonsalves (1936) reported that the thermal waters occurrence in
Caldas Velhas (Goiás State) was realized in 1722. The thermal spas
were gradationally constructed in Brazil for therapeutic and leisure
purposes, corresponding the period elapsed between the 1930s and
1950s to the most auspicious hydrothermal period in the country
(Mourão, 1992). The Brazilian Code of Mineral Waters (BCMW) was
established in this time, under French influence, by Register 7841
published on 8 August 1945 (DFPM, 1966). This rule is still in force
without any actualization, focusing the mineral waters for spas and
bottling uses, as well the potable waters for bottling (Serra, 2009).
* Tel.: þ55 19 35269244; fax: þ55 19 35249644.
E-mail addresses: danielbonotto@yahoo.com.br, danielmarcosbonotto@gmail.
com.
ters is managed by the National Department of Mineral Production
(DNPM). Traditionally, the mineral waters had been used or directly
consumed in the springs, where touristic centers developed around.
However, in the present days, the mineral water for consumption is
distributed in vessels for ingestion distant from the springs, whereas
hydrothermal spas for therapeutic baths and leisure exhibit infra-
structure with hotels and many facilities for users.
The first available information about the production of bottled
mineral waters in Brazil dates back 1911 (CPRM, 2012). Only Minas
Gerais and Rio de Janeiro States had industries by that time, whose
annual production was 1,420,000 L (Minas Gerais- 1,220,000 L; Rio
de Janeiro- 200,000 L) (CPRM, 2012). However, an accentuated
expansion of the national production occurred in the period be-
tween 1996 and 2007, i.e. North region (þ386%), West Central re-
gion (þ287%), South region (þ207%), Northeastern region (þ130%)
and Southeastern region (þ127%) (CPRM, 2012). The Southeastern
region in 2007 was responsible by about 48% of the national pro-
duction of mineral and potable water, the highest in the country
(2.08 billion liters) (CPRM, 2012). São Paulo State presented a
production superior to 1.5 billion liters in 2007, corresponding to
34% of the total in the country, followed by the states of Rio de
Janeiro (7%) and Minas Gerais (6%) (CPRM, 2012). In general terms,
circa 20 million consumers are involved (SEBRAE, 2012).

0265-931X/$ e see front matter Ó 2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jenvrad.2014.01.005
22 D.M. Bonotto / Journal of Environmental Radioactivity 132 (2014) 21e30

Many spring waters in Brazil do not contain high concentrations

of dissolved constituents, but the waters are considered mineral
due to the radioactivity in them, chiefly due to the presence of
dissolved radon (222Rn) and thoron (220Rn) (DFPM, 1966). 222Rn
(half-life 3.82 days) and 220Rn (half-life 55.6 s) are noble gas iso-
topes belonging to the 238U (4n þ 2) and 232Th (4n) decay series,
respectively. 222Rn is produced by a-decaying 226Ra and reaches the
stable 206Pb, whereas 220Rn is generated by a-emitting 224Ra,
forming the stable 208Pb (Clayton, 1983; Chu et al., 1999). Some
222
Rn and 220Rn fraction escapes from the rocks and minerals to the
surrounding fluid phase, such as groundwater and air, whose pro-
portion depends on factors such as total surface area of solids and
the concentration (and distribution) of 238U (226Ra) and 232Th
(224Ra) in them (Flügge and Zimens, 1939).
Potential health hazards from natural radionuclides in
consuming water have been considered worldwide, with many
countries adopting the guideline activity concentration for drinking
water quality recommended by WHO (2011). In general, the rec-
ommendations apply to routine operational conditions of water-
supply systems, however, special attention must be also given to
mineral waters frequently ingested by population. Thus, the
approach for radioactivity in the BCMW (DFPM, 1966) is contra-
dictory to that focused by WHO (2011).
Another relevant aspect in this situation is the lack of confident
data on the 222Rn and 220Rn activity concentration in Brazilian
spring waters, mainly for 220Rn. The available 222Rn data in some Fig. 1. Sketch map of the research region in Brazil and location of the groundwater
cases is partially a consequence of the timescale of its half-life that sampling points in the following cities of São Paulo and Minas Gerais states:
ASP ¼ Águas de São Pedro, ADL ¼ Águas de Lindóia, SEN ¼ Serra Negra, LIN ¼ Lindóia,
is longer than that of the 220Rn. This paper describes a comparative
TEI ¼ Termas de Ibirá, ASB ¼ Águas de Santa Bárbara, ADP ¼ Águas da Prata, PDC ¼
study of well-known Brazilian mineral waters occurring at São Poços de Caldas, PRV ¼ Pocinhos do Rio Verde, LAM ¼ Lambari, SLO ¼ São Lourenço,
Paulo and Minas Gerais states that was held for evaluating the CAM ¼ Cambuquira, CAX ¼ Caxambu, AXA ¼ Araxá.
presence of the following dissolved gases: 222Rn, 220Rn, O2, CO2 and
H2S. With exception of oxygen, all other gases are taken into ac-
count in the BCMW (DFPM, 1966) that has been utilized on the data generally realizes through fractures and the flow is from the higher
evaluation. The radiation dose due to the presence of dissolved to lower altitudes (del Rey, 1989), leaching migmatite (Lindália and
222
Rn and 220Rn has been calculated as both radionuclides are Santa Isabel), quartzite (Comexim, Curie, Filomena and Beleza) and
health threat when ingested in water in activity concentrations milonite/quartzite (São Roque).
exceeding the guideline reference values. Águas da Prata, Poços de Caldas and Pocinhos do Rio Verde cities
are geologically situated in the Poços de Caldas alkaline complex
2. Study area that is a ring structure of Mesozoic age, comprising a suite of
alkaline volcanic and plutonic rocks, mainly phonolites and neph-
The groundwater samples (75) for dissolved gases analyses were eline syenites (Schorscher and Shea, 1992). Seven springs were
taken from springs and pumped tubular wells drilled at different sampled at Águas da Prata city: Villela (discharges into a well
aquifer systems that are inserted in Paraná and Southeastern Shield silicified and lightly folded sandstone), Vitória (discharges through
hydrogeological provinces (Fig. 1 and Table 1). fissures in diabase), Platina (discharges in outcropping phonolites),
Águas de São Pedro, Águas de Santa Bárbara and Termas de Ibirá Prata (discharges in diabase), Boi (discharges in a silicified and
cities are inserted in the intercratonic Paraná sedimentary basin, in recrystallized sandstone), Paiol and Padre (discharges through
which the sedimentary sequence covers since the Silurian- volcanic tuffs, phonolites and eudialite-bearing nepheline syenites)
Devonian up to the Cretaceous periods (IPT, 1981). The sampling (Szikszay, 1981). Groundwater at Poços de Caldas area has been
point at Águas de Santa Bárbara city corresponded to a 120 m-deep mainly exploited in crystalline fractured rocks due to the better
tubular well that cut the Serra Geral and Botucatu formations of the yielding of the wells, but it also occurs in diffuse and punctual
Paraná sedimentary basin. The waters of Águas de São Pedro city thermal and non-thermal springs that discharge at the depression
provided from tubular wells drilled at the Tubarão Group (Paraná in Poços de Caldas city (Cruz, 1987; Cruz and Peixoto, 1989).
basin) in 1936 by DNPM (National Department of Mineral Pro- The geological substrate of Lambari, São Lourenço, Cambuquira
duction) for petroleum exploration (Kimmelmann et al., 1987). and Caxambu cities in south of Minas Gerais State comprises rocks of
However, such water sources have been popularly referred to the Proterozoic times like ophthalmic biotite gneisses, migmatized
Gioconda (Tubarão Group depth ¼ 275e625 m), Juventude granitoids, protomilonites and milonite gneisses, migmatized
(Tubarão Group depth ¼ 240e469 m) and Almeida Salles (Tubarão garnet-biotite-gneisses, metabasites intercalations secondarily cut
Group depth ¼ 207e329 m) “springs” (Kimmelmann et al., 1987). by pegmatoids veins and schists. There is also the presence of very
Águas de Lindóia, Serra Negra and Lindóia cities are located in a weathered quartzites and Quaternary alluvial deposits (CPRM, 1999).
region characterized by the occurrence of several phases and cycles, The hydrogeological model for mineral waters occurring in São
involving different aspects of metamorphism, deformation and Lourenço, Lambari and Caxambu cities involves the rainwater infil-
magmatism that acted from the Archean to the Upper Proterozoic tration in weathered horizons of gneissic rocks at the more elevated
times and affected rocks characterized by high metamorphic grade, topographic areas close to the springs (CPRM, 1999). Then, this is
generally of granulite and amphibolite facies (Ebert, 1955; Almeida succeeded by percolation through milonitized zones (São Lourenço,
and Hasui, 1984). The water circulation at Águas de Lindóia city Caxambu, and Lambari) and fractures partially filled by pegmatoids
 D.M. Bonotto / Journal of Environmental Radioactivity 132 (2014) 21e30 23

Table 1
Description of the groundwater samples analyzed in this paper.

City (Statea) Spring (well) Hydrogeological Dominant flow Major rock types Geological context/age Commercializationc
name/Sample code Provinceb

Águas de São Almeida Salles/ALS Paraná Porous Sandstones Botucatu Fm. (Jurassic)
Pedro (SP) Gioconda/GIO Pirambóia Fm. (Triassic)
Juventude/JUV Itararé Fm. (Permian)
Irati Fm. (Permian)

Águas da Platina/PLA Paraná Fractures Diabases Botucatu Fm. (Jurassic) Yes

Prata (SP) Paiol/POL Phonolites Serra Geral Fm.
(Jurassic-Cretaceous)
Vitória/VIT Alkaline rocks Poços de Caldas
intrusive complex
Boi/BOI Silicified sandstones (Cretaceous)
Prata/PTA Yes
Villela/VIL
Padre/PDE

Águas de Santa Isabel/SIL Paraná Fractures Granites Amparo Gp. Yes

Lindóia (SP) (Lower Proterozoic)
Filomena/FIL Gneisses
Beleza/BEL Migmatites
São Roque/SRE Schists
Comexim/COM Quartzites Yes
Lindália/LIN Limestones Yes
Curie/CUR Dolomites
Serra São Jorge/SJO
Negra (SP) São Carlos/SCA
Italianos/ITA
Santa Luzia/SLU
Santo Agostinho/SAT
Brunhara/BRU
Laudo Natel/LAN
Sant’Anna/SAA
Lindóia (SP) São Benedito/SBE Yes
Bioleve/BIO Yes

Termas de Jorrante/JOR Paraná Porous and Sandstones Bauru Gp. (Cretaceous)

Ibirá (SP) Ademar de Barros/ADB Fractures Basalts Serra Geral Fm.
(Jurassic-Cretaceous)
Carlos Gomes/CGO
Saracura/SRC
Seixas/SEI

Águas de Santa Balneário Paraná Porous and Sandstones Bauru Gp. (Cretaceous)
Bárbara (SP) Municipal/BMU Fractures Basalts Serra Geral Fm.
(Jurassic-Cretaceous)
Lambari (MG) No. 1/LA1 Southeastern Porous and Ortogneisses Paraíba do Sul Gp.
shield fractures (Proterozoic)
No. 2/LA2 Granulites Barbacena Gp.
(Proterozoic)
No. 3/LA3 Migmatites São João dél Rei Gp.
(Proterozoic)
No. 4/LA4 Metassedimentary Andrelândia Gp.
seq. (Proterozoic)
No. 5/LA5 Metavulcanossedimentary magmatic plutonic
seq. series (Brasiliano)
No. 6/LA6
São Lourenço No. 7-Bis/SL7
(MG) No. 5-Alcalina/SL5
No. 6-Sulfurosa/SL6
No. 3-Vichy/SL3
No. 4-Ferruginosa/SL4
No. 1-Oriente/SL1
No. 10-Primavera/SL10
No. 9-Carbogasosa/SL9
Cambuquira Roxo Rodrigues/ROR
(MG) Regina Werneck/REW
Com. Augusto
Ferreira/CAF
Fernandes Pinheiro/FEP
Marimbeiro/MAR
Souza Lima/SLI
Caxambu Geiser Floriano
(MG) de Lemos/GFL
Venâncio/VEN
Mayrink/MAY
(continued on next page)
24 D.M. Bonotto / Journal of Environmental Radioactivity 132 (2014) 21e30

Table 1 (continued )

City (Statea) Spring (well) Hydrogeological Dominant flow Major rock types Geological context/age Commercializationc
name/Sample code Provinceb

Ernestina Guedes/EGU
Viotti/VIO
D. Pedro II/DPE
Beleza/BZA
Duque de Saxe/DXE
Da. Leopoldina/LEO
Da. Isabel/Conde dÉu/ISA

Poços de Quisisana/QUI Southeastern Fractures Alkaline rocks Poços de Caldas

Caldas (MG) shield intrusive complex
XV de Novembro/NOV Nepheline syenites (Cretaceous)
Macacos/MAC Phonolites
Sinhazinha/SIN Pyroclastics
Frayha/FRA Volcanic tuffs
Pedro Botelho/PEB
Pocinhos do Rio Verde/RIV
Rio Verde (MG) Samaritana/SMA
São José/SJO
Amorosa/AMO

Araxá (MG) Dona Beja/DBJ Southeastern Porous and Quartzites and schists Cretaceous
Andrade Júnior/AJU shield fractures Alkaline-carbonatitic rocks PreCambrian
a
SP ¼ São Paulo, MG ¼ Minas Gerais.
b
According to Mente (2008).
c
Water commercialized by private company in addition to consumption in taps accessible to population in public areas.

dykes or alkaline breccias (Caxambu) (CPRM, 1999). The local con-
ditions favor the periodical eruption (up to 5-m height) of a non-
geothermal geyser at the Caxambu waterpark due to the build-up
of pressure from dissolved carbon dioxide in the water.
Araxá city is geologically located at Alto Paranaíba Igneous
Province that includes the renowned carbonatite intrusion of
Araxá, which covers approximately 16 km2 and is in general related
to a NW-trending linear structure bordering the São Francisco
cratonic area that is thought to be in evidence since late Precam-
brian times (Traversa et al., 2001). Two springs were sampled at
Araxá city: 1) Dona Beja, associated to an aquifer system classified
as granular, free and semi-confined, mainly in the intrusive body
domain (Beato et al., 2000); 2) Andrade Júnior, related to a deep
fractured aquifer, unconfined to semi-confined, mainly occurring in
rocks surrounding the carbonatite complex (Beato et al., 2000).
3. Sampling and analytical methods
The sampling points (75) were chosen according to the hydro-
chemical information from previous studies and to the easy access
for collection. The groundwater chemical composition is attained
due to processes occurring at the liquidesolid interface when
different rock matrices are extensively leached.
The sampling sites were (Fig. 1 and Table 1): Águas de São Pedro
(3 water sources), Águas da Prata (7 water sources), Águas de Lindóia
(7 water sources), Serra Negra (8 water sources), Lindóia (2 water
sources), Termas de Ibirá (5 water sources), Águas de Santa Bárbara
(1 water source), Lambari (6 water sources), São Lourenço (8 water
sources), Cambuquira (6 water sources), Caxambu (10 water sour-
ces), Poços de Caldas (6 water sources), Pocinhos do Rio Verde (4
water sources) and Araxá (2 water sources). All water sources
(except geyser “Floriano de Lemos”, Caxambu city) have been used
for drinking purposes in thermal and non-thermal spas and some of
them are commercialized by private companies (Table 1).
The sampling campaign occurred between March and June 2012
(autumn), when the local air temperature was often lower than that
of the summer months (average in January ¼ 30e32  C). The
rainfall was lower than that of the wet season (summer,
DecembereJanuary) but higher than that of the dry season (winter,
JulyeAugust).
About 500 mL of groundwater sample was directly taken from
taps/pipes installed in each spring/well, which was stored in glass/
plastic flasks of variable volume as required by each gas (222Rn,
220
Rn, O2, CO2 and H2S) analysis. Temperature was also measured
by the use of a digital portable meter in addition to the dissolved
gases readings. All data acquisition was in situ performed for
avoiding gases losses and modification of other physical and
chemical parameters of the waters.
The dissolved oxygen (DO) concentration was determined in a
digital portable meter recording the potential values generated by an
O2 sensible electrode consisting on a metallic wire covered by a thin
gold layer (detection limit ¼ 0.1 mg/L). The electrode was inserted
into a 60-mL Winkler bottle filled with the water sample, then, the
final value was recorded after stabilization of the reading. All DO data
were corrected due to differences in altitude of the sampling points,
using as reference the value corresponding to the sea level.
The carbon dioxide was evaluated by the buret titration method
on using water volumes of 25 or 50 mL (Hach, 1992). This amount
was inserted in a clean erlenmeyer flask, then, one powder pillow
of a phenolphthalein indicator solution (5 g/L) (Hach, 1992) was
added and the solution mixed gently. A 25-mL buret was filled to
the zero mark with 0.0227 N NaOH solution and the prepared
sample was titrated while gently swirling the flask until a light pink
color formed and persisted for 30 s. The reaction of NaOH with CO2
(as carbonic acid) occurs in two steps, first a reaction from carbonic
acid to bicarbonate and then to carbonate. Because the conversion
of CO2 to bicarbonate is complete at pH 8.3, phenolphthalein was
used as a color indicator for the titration (Hach, 1992). The dissolved
CO2 (in mg/L) was calculated on multiplying the volume (in mL) of
the titrant used by the factor 20 (sample volume ¼ 50 mL; detection
limit ¼ 2 mg/L) or 40 (sample volume ¼ 25 mL; detection
limit ¼ 4 mg/L) (Hach, 1992). The pink color in some samples was
immediately formed with the addition of the phenolphthalein in-
dicator. The dissolved CO2 corresponded to 0 mg/L in these cases as
it was not necessary the addition of the titrant (0.0227 N NaOH
solution) for the color change.
The dissolved sulfide gas was determined by colorimetry
(wavelength 665 nm) using a program stored in the Hach DR/2000
spectrophotometer (Hach, 1992). The methylene blue method was
adopted in which the hydrogen sulfide and acid-soluble metal
 D.M. Bonotto / Journal of Environmental Radioactivity 132 (2014) 21e30
sulfides react with N,N-dimethyl-p-phenylenediamine oxalate to
form methylene blue (Hach, 1992). One glass cell (the prepared
sample) was filled with 25 mL of sample, whereas another (the
blank) was filled with 25 mL of deionized water. Then, 1 mL of
Sulfide 1 Reagent (N,N-dimethyl-p-phenylenediamine oxalate) was
added to each cell and, after mixing, 1 mL of Sulfide 2 Reagent
(potassium dichromate) was put into both cells. After mixing and a
5-minute reaction time, the blank was inserted into the cell holder,
the spectrophotometer was set to zero reading, the prepared
sample was placed into the cell holder and the equipment dis-
played the result in mg/L sulfide (S2) (Hach, 1992). The intensity of
the blue color was proportional to the sulfide concentration and
proper dilution was used to determine high sulfide levels is some
samples. The detection limit of the method corresponded to 1 mg/L
sulfide.
The radon and thoron dissolved in water were analyzed on site
using RAD7 alpha particles detector coupled to accessory RADH2O
from Durridge Co. The RAD7 utilizes a solid state alpha detector,
comprising a Si semiconductor material that converts the energy of
the alpha particles into an electrical signal. The accumulation of
many signals results in a spectrum that is presented on a scale of
alpha energy in the range of 0e10 MeV. Such energy interval is
suitable for 222Rn and 220Rn readings as data acquisition takes place
between 6 and 9 MeV (Durridge, 2009a). The spectrum is displayed
in a set of 200 channels grouped into eight windows of different
energy range. A, B, C and D are the main windows, whereas E, F, G
and H are the diagnostic of main windows. Windows A and C
provide 222Rn activity concentration data from 218Po and 214Po
decays, representing “new” (218Po) and “old” (214Po) 222Rn,
respectively (Durridge, 2009a). Windows B and D provide 220Rn
activity concentration data from 216Po and 212Po decays, repre-
senting “new” (216Po) and “old” (212Po) 220Rn, respectively
(Durridge, 2009a). Thus, the RAD7 separates the radon and thoron
signals by energy of the alpha particles from their progeny,
becoming possible to measure both Rn isotopes simultaneously
(Durridge, 2009a). The equipment was factory calibrated by way of
inter-comparison with radon chambers run by the U.S. EPA and the
U.S. Department of Energy (Durridge, 2009a).
The groundwater samples were collected in 100-mL flasks,
avoiding as much as possible the exposure to atmospheric air. The
RADH2O accessory unit employed an aeration system in a closed
circuit connecting the sample, RAD7 and a desiccant tube con-
taining Drierite to humidity absorption (Durridge, 2009b). Then,
the air circulated through the sample during about 10 min,
extracting radon and thoron until reaching an equilibrium state (for
readings in windows A and B). The radon and thoron extracted
were pumped into the RAD7, where their progeny were detected.
The instrument display recorded the dissolved 222Rn and 220Rn
activity concentration data in pCi/L that were converted to the SI
unit (Bq/L for 222Rn and mBq/L for 220Rn). The Detection Limit (DL)
corresponded to 4 mBq/L (Durridge, 2009a), whereas the un-
certainties given of the results were one standard deviations,
resulting from propagation of all statistical uncertainties in the
entire measurement process. The low activity concentration in
some samples implied on high analytical uncertainty as reported
elsewhere (for instance, Jia et al., 2002).
4. Results and discussion
4.1. Temperature and dissolved oxygen, carbon dioxide and sulfide
in the waters
The groundwater temperature ranged from 20.4 to 35.7  C
(mean ¼ 24.8  C) (Table 2). According to the BCMW guidelines for
temperature (DFPM, 1966), three categories can be defined for the
25
analyzed waters: cold (values lower than 25  C ¼ 41 samples),
hypothermal (values ranging from 25 to 33  C ¼ 33 samples) and
mesothermal (values ranging from 33 to 36  C ¼ 1 sample).
The mean dissolved oxygen (DO) concentration was 3.5 mg/L
(Table 2). The lowest DO content was 0.8 mg/L (Macacos spring,
Poços de Caldas city, Minas Gerais State), whereas the highest DO
concentration was 9 mg/L (São Benedito water source, Lindóia city,
São Paulo State) that corresponds to the solubility of oxygen at 100%
air saturation at 21  C and 760 mmHg mount air barometric pres-
sure (EIFAC, 1986). The gas content (in solution) of a mass of water
can be evaluated considering the Henry’s law and Dalton’s law of
partial pressure. From both gas laws, it has been widely recognized
that the solubility of oxygen in water varies with temperature, the
DO content reducing sharply with increase in temperature (Cole,
1983; APHA, 1985; EIFAC, 1986). Treusdale et al. (1955) reported
the solubility value for oxygen at various temperature, which was
re-estimated using improved Henry coefficients (Benson and
Krause, 1980) as discussed by Cole (1983). The values of solubility
of oxygen in water at various temperatures, from moist air at
760 mmHg at 0.0 ppt salinity, taken from EIFAC (1986) is 9.1 mg/L at
21  C and 6.9 mg/L at 35  C. There is a significant inverse rela-
tionship between temperature and dissolved O2 in the analyzed
groundwater (Fig. 2a), confirming that the increase in temperature
causes a decrease in dissolved O2. The two-tailed P value estimated
by GraphPad software from the Pearson correlation coefficient
(r ¼ 0.41, n ¼ 75; Fig. 2a) equals 0.0003 by conventional criteria,
suggesting this difference is extremely statistically significant.
The mean dissolved CO2 concentration was 590 mg/L (Table 2).
The dissolved CO2 was absent in nine samples, from which five
were collected at Termas de Ibirá city in São Paulo State. Degassing
favored by cracks, faults and fissures in basalts of the Serra Geral
Formation may be a possible reason for the null CO2 values at
Termas de Ibirá city. The dissolved CO2 ranged from 52 to 1840 mg/
L in the remaining samples (Table 2) and its presence in waters is
mainly related to the carbonates dissolution in the rock matrices.
The groundwater temperature range is from 25 to 35.7  C in the
hypothermal and mesothermal waters (Table 2) and such large
difference (10.7  C) favors the significant inverse relationship be-
tween temperature and dissolved carbon dioxide (Fig. 2b), indi-
cating that its solubility decreases accompanying the temperature
raising as also verified for oxygen. The two-tailed P value estimated
by GraphPad software from the Pearson correlation coefficient
(r ¼ 0.49, n ¼ 34; Fig. 2b) equals 0.0033 by conventional criteria,
suggesting this difference is very statistically significant.
According to the BCMW guidelines, the carbogaseous waters
contain dissolved carbon dioxide gas corresponding to a minimum
of 200 mL per liter of water (DFPM, 1966). The CO2 concentration
data in Table 2 can be used for estimating the CO2 volume (in mL)
per liter of water from the ideal gas law that is the state equation of
a hypothetical (ideal) gas. Although it has limitations, it is a rough
approximation to the behavior of some gases like CO2, under some
conditions. It is often written as PV ¼ nRT where P is the gas
pressure, V is the gas volume, n is the gas number of moles, T is the
gas temperature and R is the ideal, or universal, gas constant. If T is
expressed in Kelvin, then, R ¼ 0.0821 L.atm/K.mol. Remembering
that 1 mol CO2 corresponds to approximatelly 44 g, then, it is
possible estimate V values (in mL) varying from 0 to 1025 mL
(Table 2).
The comparison of the V values (in mL) for CO2 in Table 2 with
the BCMW guideline of 200 mL per liter of water (DFPM, 1966)
indicates that 33 water sources are carbogaseous. However, some of
them are popularly recognized by other chemical attributes rather
than dissolved CO2, for instance: No. 2 (Lambari city) and No. 5 (São
Lourenço city) are said alkaline waters; No. 3 (Lambari city) and
Com. Augusto Ferreira (Cambuquira city) are said magnesian
26 D.M. Bonotto / Journal of Environmental Radioactivity 132 (2014) 21e30

Table 2
Temperature, dissolved gases, radon and thoron data in groundwater samples analyzed in this paper.

Sample codea Temp. ( C) O2 (mg/L) CO2 (mg/L) CO2 (mL)b H2S (mg/L) 222
Rn (Bq/L)c 220
Rn (mBq/L)c 222
Rn (  105 J/yr)d 220
Rn (  105 J/yr)d

ALS 27.1 3.13 120 67.2 0.003 1.4  0.2 52  63 0.55 0.29
GIO 27.4 5.08 100 56.1 0.006 1.7  0.2 <4 0.68 <0.02
JUV 26.7 2.81 88 49.2 3.064 0.02  0.02 <4 0.01 <0.02
PLA 25.4 1.33 400 222.8 0.005 24.4  1.2 270  185 9.91 1.50
POL 25.8 3.06 800 446.2 0.012 4.8  0.5 200  144 1.95 1.11
VIT 24.5 1.33 1032 573.2 0.002 53.3  1.8 63  81 21.60 0.35
BOI 24.2 3.77 128 71.0 0.004 74.7  2.2 52  63 30.30 0.29
PTA 25.1 7.14 180 100.2 0.004 23.2  1.2 70  74 9.43 0.39
VIL 24.3 5.71 140 77.7 0.003 104.3  3.3 226  185 42.30 1.25
PDE 23.7 5.10 256 141.8 0.004 5.6  0.6 255  148 2.28 1.42
SIL 22.5 5.35 96 53.0 0.001 22.1  1.1 15  22 8.96 0.08
FIL 26.9 4.65 108 60.5 0.002 7.8  0.6 200  137 3.17 1.11
BEL 26.4 3.84 88 49.2 0.002 8.3  0.7 67  70 3.36 0.37
SRE 27.3 4.44 164 91.4 0.002 5.0  0.5 <4 2.01 <0.02
COM 23.6 6.06 100 55.4 0.001 6.0  0.6 15  22 2.42 0.08
LIN 24.6 5.66 136 75.6 0.004 7.4  0.6 226  144 2.99 1.25
CUR 26.2 4.65 128 71.5 0.005 9.2  0.7 89  85 3.74 0.49
SJO 22.0 6.16 132 72.7 0.002 10.0  0.7 7  11 4.04 0.04
SCA 21.7 5.66 236 129.8 <0.001 10.8  0.7 15  22 4.37 0.08
ITA 20.4 5.66 212 116.1 0.008 5.8  0.6 26  37 2.36 0.14
SLU 21.5 2.83 188 103.4 0.001 25.0  1.2 181  133 10.15 1.01
SAT 21.8 3.23 236 129.9 0.002 31.4  1.4 240  148 12.74 1.33
BRU 22.1 4.85 160 88.1 0.001 30.2  1.3 418  222 12.24 2.32
LAN 23.1 3.64 212 117.2 0.003 6.2  0.6 15  26 2.51 0.008
SAA 21.9 4.65 200 110.1 0.001 23.9  1.1 26  37 9.72 0.14
SBE 24.9 9.05 180 100.1 0.003 10.3  0.7 56  63 4.17 0.31
BIO 23.6 6.45 132 73.1 0.003 2.4  0.4 <4 0.98 <0.02
JOR 26.8 2.05 0 0 0.013 0.5  0.1 <4 0.20 <0.02
ADB 27.2 2.59 0 0 0.003 2.7  0.4 26  41 1.10 0.14
CGO 28.4 1.30 0 0 0.005 3.4  0.4 26  33 1.36 0.14
SRC 28.7 0.97 0 0 0.035 3.6  0.4 26  41 1.46 0.14
SEI 26.4 2.38 0 0 0.008 2.4  0.3 <4 0.97 <0.02
BMU 24.6 5.99 252 140 0.002 1.3  0.2 26  37 0.54 0.14
LA1 23.0 5.00 1840 1016.8 0.001 8.2  0.6 78  81 3.32 0.43
LA2 23.0 4.69 1600 884.1 0.002 10.3  0.7 259  148 4.19 1.44
LA3 23.1 4.49 1480 818.1 0.001 13.5  0.8 237  148 5.48 1.31
LA4 24.0 4.69 600 332.7 <0.001 9.6  0.7 81  81 3.89 0.45
LA5 25.4 6.73 1840 1025.0 <0.001 7.9  0.6 26  37 3.20 0.14
LA6 24.0 5.51 1480 820.6 <0.001 8.5  0.7 44  56 3.44 0.25
SL7 24.7 1.53 800 444.6 0.018 1.6  0.3 22  30 0.67 0.12
SL5 23.6 1.73 1560 863.8 <0.001 1.1  0.2 48  56 0.44 0.27
SL6 25.2 1.22 1720 957.5 <0.001 4.1  0.4 41  52 1.68 0.22
SL3 26.7 3.67 1320 738.5 <0.001 4.4  0.5 78  78 1.80 0.43
SL4 26.6 1.94 920 514.6 <0.001 4.0  0.4 33  44 1.64 0.18
SL1 25.6 1.33 1420 791.6 <0.001 0.9  0.2 33  44 0.37 0.18
SL10 25.2 3.06 1200 668.0 <0.001 4.8  0.6 41  52 1.95 0.22
SL9 23.9 1.02 1480 820.3 <0.001 3.6  0.4 52  59 1.44 0.29
ROR 24.0 3.74 800 443.6 0.001 1.5  0.3 92  92 0.62 0.51
REW 24.0 3.03 1380 765.1 0.003 4.6  0.5 333  185 1.85 1.85
CAF 26.3 4.34 1000 558.7 0.001 3.0  0.4 100  89 1.21 0.55
FEP 25.0 2.63 1760 979.1 0.040 13.4  0.9 67  74 5.42 0.37
MAR 25.5 3.33 1200 668.7 0.004 1.6  0.3 218  148 0.66 1.21
SLI 23.2 3.13 1080 597.2 0.013 0.8  0.2 <4 0.32 <0.02
GFL 23.8 4.69 1100 609.5 0.014 3.0  0.4 895  333 1.21 4.97
VEN 25.0 2.86 1680 934.6 0.017 4.8  0.6 314  222 1.94 1.74
MAY 25.5 4.18 800 445.8 0.004 35.3  1.5 444  259 14.34 2.46
EGU 25.8 1.73 1600 892.5 <0.001 10.1  0.8 492  222 4.08 2.73
VIO 25.3 1.84 800 445.5 0.015 45.9  1.8 418  259 18.62 2.32
DPE 24.7 1.94 880 489.1 0.009 40.7  1.8 63  74 16.52 0.35
BZA 23.9 1.84 1440 798.1 0.001 6.9  0.7 385  222 2.79 2.13
DXE 25.4 1.84 720 401.1 0.007 8.0  0.7 192  144 3.23 1.07
LEO 24.5 1.02 680 377.7 0.047 18.4  1.1 81  85 7.48 0.45
ISA 24.2 1.53 920 510.4 0.010 5.3  0.6 148  122 2.15 0.82
QUI 22.4 2.25 104 57.4 0.001 8.4  0.7 52  67 3.41 0.29
NOV 25.7 1.37 0 0 0.259 16.2  0.9 96  89 6.58 0.53
MAC 32.1 0.78 0 0 1.184 2.0  0.3 <4 0.82 <0.02
SIN 25.7 2.94 140 78.1 0.003 35.5  1.4 522  259 14.40 2.89
FRA 23.2 3.82 52 28.8 <0.001 23.2  1.2 866  296 9.40 4.80
PEB 35.7 1.18 0 0 0.383 17.6  1.0 292  185 7.15 1.62
RIV 23.3 1.30 180 99.6 0.756 36.3  1.5 81  85 14.75 0.45
SMA 23.9 1.40 80 44.3 0.522 10.4  0.8 178  141 4.20 0.98
SJO 22.0 1.30 60 33.0 0.528 41.1  1.5 89  89 16.67 0.49
AMO 21.7 5.80 112 61.6 0.004 31.4  1.4 15  26 12.73 0.08
DBJ 22.1 5.00 252 138.8 0.001 112.5  3.0 141  133 45.65 0.78
 D.M. Bonotto / Journal of Environmental Radioactivity 132 (2014) 21e30
Table 2 (continued )
Sample codea Temp. ( C) O2 (mg/L) CO2 (mg/L) CO2 (mL)b
AJU 29.0 1.60 0 0
Min. 20.4 0.78 0 0
Max. 35.7 9.05 1840 1025
Mean 24.8 3.46 590 328
SDe 2.4 1.83 597 332
a
For sample description, see Table 1.
b
Volume of dissolved CO2 per liter of water.
c
Analytical uncertainty corresponding to 1s standard deviation.
d
Annual potential a-energy intake (UNSCEAR, 2006).
e
SD ¼ Standard Deviation.
waters; No. 5 (Lambari city), No. 4 (São Lourenço city) and Fer-
nandes Pinheiro (Cambuquira city) are said ferruginous waters; No.
6 and No. 7 Bis (São Lourenço city) and Souza Lima (Cambuquira
city) are said sulfured waters.
Carbogaseous springs exhibiting free CO2 content over 250 mg/L
have been recognized elsewhere, for instance, Daylesford
(Australia), Bad Gleichenburg (Austria), Vichy (France), Bad Ems
(Germany), Bath (England), Balatonfüred (Hungary), Hvergerdi
(Iceland), Chianciano Terme (Italy), Narugo (Japan), Yura (Peru),
Pedras Salgadas (Portugal), Pyatigorsk (Russia), Rogaska (Slovenia),
Rheinfelden (Switzerland) and Saratoga Springs (USA) (Altman,
2000). In Spain, a study was held by Eyzaguirre (2003) that
involved 12 field trips summing up to 15,056 km and encompassed
analytical determinations for 95 Spanish mineral-medicinal waters
from 82 balnearies. Carbogaseous waters were recognized for only
8 water sources, which possessed CO2 contents between 253 mg/L
(Mondariz-Gándara, Pontevedra) and 742.5 mg/L (Laranjón-Capilla,
Granada) (Eyzaguirre, 2003). Table 2 shows that 29 groundwater
samples analyzed in this paper contain dissolved CO2 higher than
742.5 mg/L that is the maximum value found by Eyzaguirre (2003).
The dissolved H2S concentration was below the detection limit
of the spectrophotometric method (1 mg/L) in 13 groundwater
samples (Table 2). The remaining water sources contained between
0.001 and 3.06 mg/L of dissolved sulfide. Contrarily to O2 and CO2,
no significant relationship was found between temperature and
dissolved sulfide in the analyzed waters. According to the BCMW
guidelines, the sulfured waters contain dissolved sulfur corre-
sponding to a minimum of 0.001 g per liter (¼1 mg/L) (DFPM, 1966).
This only happened for the following waters (Table 2): Juventude
(Águas de São Pedro city), Macacos (Poços de Caldas city) and
Andrade Júnior (Araxá city). However, other water sources have
been also popularly named as sulfured despite they do not strictly
adhere to the BCMW guideline of 1 mg/L, i.e.: Rio Verde (0.76 mg/L),
Samaritana (0.52 mg/L) and São José (0.53 mg/L) at Pocinhos do Rio
Verde city; XV de Novembro (0.26 mg/L) at Poços de Caldas city;
Souza Lima (0.01 mg/L) at Cambuquira city; No. 6 (<0.001 mg/L)
and No. 7 Bis (0.018 mg/L) at São Lourenço city. In Spain, sulfured
waters were recognized by Eyzaguirre (2003) in 21 water sources,
which possessed H2S contents between 1.3 mg/L (Laias, Orense)
and 36.8 mg/L (Fuente Amarga, Cádiz), most of them well above the
maximum value found in this paper (3 mg/L).
4.2. Dissolved radon and thoron in the waters
The 222Rn activity concentration ranged from 0.02 to 112.5 Bq/L,
whereas the 220Rn activity concentration range was <4e895 mBq/
L) (Table 2).
Numerous papers are available on the determination of radon in
mineral waters, some of them pointing to the use of treatments
involving the intake of radon gas through inhalation or by trans-
cutaneous resorption of radon dissolved in water. For instance,
natural and artificial grottoes carved in the rock bathing tubs found
27
H2S (mg/L) 222
Rn (Bq/L)c 220
Rn (mBq/L)c 222
Rn (  105 J/yr)d 220
Rn (  105 J/yr)d
1.980 7.0  0.6 26  37 2.82 0.14
<0.001 0.02 <4
3.064 112.5 895
0.121 15.4 141
0.447 20.9 178
in some of the oldest spas in Central and Southern Europe have
been considered by Zdrojewicz and Strzelczyk (2006) who reported
high 222Rn levels of 2000e4000 Bq/L at the island of Ischia in the
volcanic area near Naples, Merano and Lurisia spas in the alpine
region (Italy). In Spain, radioactive waters (222Rn activity concen-
tration higher than 67.3 Bq/L) were recognized by Eyzaguirre
(2003) in 24 water sources that exhibited 222Rn levels between
73 Bq/L (Caldas de Boí-Tartera, Lérida) and 1868 Bq/L (Arnedillo, La
Rioja). In this paper, the highest 222Rn levels (75e112 Bq/L) were
found in Boi and Villela springs located at Águas da Prata city (São
Paulo State) and Dona Beja spring situated at Araxá city (Minas
Gerais State) that are well below of many values reported by
Eyzaguirre (2003) and Zdrojewicz and Strzelczyk (2006).
In contrast to the abundant reports focusing 222Rn in mineral
waters, only a few studies have been done on the quantitative
determination of thoron, because of the difficulties in measuring
the radioactivity of a gaseous isotope with a half life of w56 s.
Among the exceptions is the investigation held by Misdaq and
Chaouqi (2008) who measured the 220Rn activity concentration in
13 bottled mineral water samples from Morocco, France, and Italy
widely consumed by the European population living in Marrakech
city (Morocco). Misdaq and Chaouqi (2008) reported 220Rn levels
ranging from 0.91 to 3.4 Bq/L that are above of the values found in
this paper (<0.004e0.9 Bq/L; Table 2).
Thus, in this paper, the highest 222Rn levels were found in
springs situated at Águas da Prata city (São Paulo State) and Araxá
city (Minas Gerais State). Águas da Prata city is placed in the border
of the Poços de Caldas alkaline complex that is a well-known massif
characterized by the presence of high natural radioactivity
(Bonotto, 2010). It comprises a suite of alkaline volcanic and
plutonic rocks (mainly phonolites and nepheline syenites) which
accumulate the natural radioelements uranium and thorium and
rare-earth elements (REEs) (Schorscher and Shea, 1992). In Araxá
city, Dona Beja spring is located at the Barreiro area, where uranium
can occur widely disseminated in the pyrochlore matrix as a trace
constituent (100 ppm U3O8) or may characterize an uraniferous
pyrochlore with the U3O8 concentration reaching up to 2% (Castro
and Souza, 1970). U3O8 contents varying between 150 and
200 ppm have also been reported in the large phosphate deposit at
Barreiro area, which has been extensively explored by Bunge (past
Serrana). Uranium also occurs associated to the REEs at the central-
northern portion of Barreiro area. The genesis of this deposit is
linked to the presence of the REEs-enriched carbonatite that
formed a closed ellipsoidal structure (Grossi Sad and Torres, 1976).
WHO (2011) proposed that controls should be implemented if
the 222Rn concentration of drinking-water for public water supplies
exceeds 100 Bq/L, i.e. treatment of the water source should be
undertaken to reduce the 222Rn levels to well below 100 Bq/L. A
comparison of this value with the results reported here indicates
that it was exceeded in Villela spring (104.3 Bq/L) and Dona Beja
spring (112.5 Bq/L) (Table 2). Both water sources are not utilized in
water-supply systems but are available for ingestion by population
28 D.M. Bonotto / Journal of Environmental Radioactivity 132 (2014) 21e30

10 and 50 Mache units per liter) and strongly radioactive (radon

content higher than 50 Mache units per liter). Thus, values below 5
Mache unit per liter indicate the waters are non-radioactive. The
conversion of the 222Rn activity concentration data given in Table 2
to Mache units yields a classification of non-radioactive for prac-
tically all waters, as the values often varies between 0.003 and
4.51 Mache unit/L. The unique exceptions are Vitória (5.24 Mache
unit/L), Boi (7.34 Mache unit/L), Villela (10.25 Mache unit/L) and
Dona Beja (11.05 Mache unit/L) springs.
Therefore, according to the BCMW guidelines (DFPM, 1966), the
waters of Vitória and Boi springs are weakly radioactive (radon con-
tent within the range of 5e10 Mache units per liter), whereas the
waters of Villela and Dona Beja springs are radioactive (radon content
within the range of 10e50 Mache units per liter). Such findings
contradict the “common sense” classification of radioactive for
several water sources studied here like: Balneário Municipal (Águas
de Santa Bárbara city); São Carlos and Italianos (Serra Negra city); Rio
Verde, Samaritana and São José (Pocinhos do Rio Verde city); Mayrink
and Viotti (Caxambu city). The data reported in Table 2 clearly in-
dicates that these waters are non-radioactive in terms of the dissolved
radon guideline established by the BCMW (DFPM, 1966).

222 220
4.3. Radiation dose due to Rn and Rn

222
Rn has been recognised, along with its decay products, to be
the most important source of exposure to natural radioactivity.
Consequently, widespread and intensive work has been conducted
on monitoring activity, research into fundamental release and
transport mechanisms, development and improvement of mea-
Fig. 2. Diagrams showing the relationship between (a) temperature and dissolved surement techniques, research on remedial actions, etc. The case of
oxygen of all analyzed waters and (b) temperature and carbon dioxide of the hypo- thoron (220Rn) is very different from that of radon as due to its short
thermal and mesothermal waters. half-life, the activity concentration generally does not reach a high
enough value for its decay products to produce significant doses.
in public areas. Despite they are just occasionally ingested, it is The low health interest in 220Rn, further evidenced by the lack of
important emphasize that some caution would be needed for their attention in some ICRP publications (for instance, ICRP, 1987, 1991)
consumption due to the high 222Rn levels. along with experimental difficulties in conducting in-field mea-
There is a significant direct relationship between dissolved surements, have, over time, increased the gap between knowledge
radon and thoron in the hypothermal and mesothermal waters about radon and thoron. Nevertheless, in certain situations, thoron
(Fig. 3). The two-tailed P value estimated by GraphPad software exposure can produce a dose comparable to that from radon.
from the Pearson correlation coefficient (r ¼ 0.72, n ¼ 34; Fig. 3) The adoption of some dose conversion factor (DCF) (IAEA, 1996;
equals 0.0001 by conventional criteria, suggesting this difference is WHO, 2011) is required to estimate committed effective doses due
extremely statistically significant. Such finding is perhaps related to
temperature effects on the dissolution of their parents 226Ra and
224
Ra from the rock surfaces. 222Rn and 220Rn would be produced
through a-decay of 226Ra and 224Ra, respectively, after their release
into the liquid phase. The dissolution processes would be favored
during the interactions involving the higher temperature waters
and the grain boundaries and/or multi-grain aggregates in rocks
and minerals. This is because they possess temperature values that
are above up to about 11  C of the lowest ones.
According to the BCMW guidelines (DFPM, 1966), the thorif-
erous waters contain dissolved thoron corresponding to a mini-
mum of 2 Mache units per liter. The equivalence that 1 Mache unit
per liter corresponds to 275 pCi/L (¼10.2 Bq/L) (UNSCEAR, 2006)
may be applied to the data set given in Table 2. Thus, it is possible
obtain 220Rn activity concentration varying between <0.0004 and
0.088 Mache unit/L, which is a range well below the reference value
of 2 Mache unit/L. Therefore, none of the waters analyzed are
thoriferous, despite people involved in the marketing and
commercialization of some waters usually consider them possess-
ing significant levels of dissolved thoron.
According to the BCMW guidelines (DFPM, 1966), the radioac-
tive waters contain dissolved radon according to three different
levels of Mache units: weakly radioactive (radon content between 5 Fig. 3. The relationship between dissolved thoron (220Rn, in mBq/L) and radon (222Rn,
and 10 Mache units per liter), radioactive (radon content between in Bq/L) in the hypothermal and mesothermal waters analyzed in this paper.
 D.M. Bonotto / Journal of Environmental Radioactivity 132 (2014) 21e30
to the radionuclides in waters. However, there is no consensus in
the literature on the DCF value for 222Rn and 220Rn. A value of
108 Sv/Bq resulting from the application of a modified ICRP model
for the 222Rn ingestion in water has been sometimes adopted
(Kendall et al., 1988; Oliveira et al., 2001; Bonotto, 2004). Bonotto
(2011) utilized DCF ¼ 1.4  106 mSv/Bq when studying the ma-
jor aquifer systems of the Paraná sedimentary basin, Brazil, which
was estimated considering the individual dose criterion of 0.1 mSv/
year (WHO, 2011) and the guideline 222Rn volumetric activity value
in drinking water of 100 Bq/L for public water supplies (WHO,
2011).
Despite several papers have been published on dosimetric
models for radon decay products, very few dosimetric studies deal
with thoron decay products. Some available dose conversion fac-
tors for them have been expressed as the effective dose (in Sv) per
unit of exposure (in J h m3). They were generally based on old
dosimetric models and on outdated values for aerosol and physi-
ological parameters (Nuccetelli and Bochicchio, 1998). OECD/NEA
(1983) assumed DCF ¼ 0.52 Sv per J h m3 for adults exposed to
220
Rn indoors, whereas for children the value was estimated to be
up to twice as high. UNSCEAR (1993) reported
DCF ¼ 0.42 Sv per J h m3, referring to all organs and tissue and
assuming an indoor occupancy factor of 100%, while the value
calculated for the lung and for an indoor occupancy factor of 80%
would be 0.35 Sv per J h m3. IAEA (1996) assumed
DCF ¼ 0.48 Sv per J h m3 that would be valid only for workers,
whereas CEU (1996) expressed DCF ¼ 0.5 Sv per J h m3 for
exposure in workplaces that was called “conventional”.
Radon and thoron decay product exposure rates have been also
specified by the measure of potential alpha energy concentration
(PAEC), given in units of J m3 and the equilibrium-equivalent
concentration (EEC), expressed in Bq m3. The PAEC is derived
from a linear combination of the activities of the short-lived decay
products in each 222Rn and 220Rn series (UNSCEAR, 2000). The
constants in the linear combination are the fractional contributions
of each decay product to the total potential alpha energy
(UNSCEAR, 2000). The EEC (in Bq m3) can be converted to the
PAEC by the relationships (UNSCEAR, 2006):
1 Bq m3 ¼ 5.56  109 J m3 for 222Rn; 1 Bq m3 ¼ 7.6  108 J m3
for 220Rn.
IAEA (1996) expressed the limits on intake for radon and thoron
progenies. The maximum in a single year of the potential a-energy
intake for radon progeny corresponds to 0.042 J, whereas for thoron
progeny is 0.127 J. Such guideline values are useful to perform a
dosimetric evaluation from 222Rn and 220Rn activity concentration
data. The values in Bq/L (Table 2) are converted into Bq/m3
(1 m3 ¼ 103 L), from which it is possible estimate the PAEC (in J m3)
for radon and thoron. WHO (2011) established guidance levels for
several radionuclides in drinking water, assuming that 730 L is the
annual ingested volume of water (equivalent to 2 L per day). The
multiplication of such amount (0.73 m3) by the PAEC for radon and
thoron yields the annual potential a-energy intake (in J yr1) for
222
Rn and 220Rn progenies (Table 2).
The maximum a-energy intake for radon progeny corresponded
to 0.4  103 J as reported in Table 2 for Villela and Dona Beja
springs. It is about 100 times lower than the guideline value of
0.042 J reported by IAEA (1996). These water sources also exhibited
the highest 222Rn activity concentration, i.e. exceeded the WHO
(2011) guideline value of 100 Bq/L. The maximum thoron progeny
intake was 5  105 J for the geyser at Caxambu city, Minas Gerais
State (Table 2). It is almost 2600 times lower than the IAEA (1996)
guideline value of 0.127 J and circa 80 times lower than the
maximum a-energy intake for radon progeny at Villela and Dona
Beja springs. Thus, 220Rn doses are much lower than that of 222Rn
what is compatible with the widespread and intensive work
29
conducted on monitoring radon elsewhere as the thoron activity
concentration generally does not reach a high enough value for its
decay products to produce significant doses.
Another significant finding is the congruency between the
highest 222Rn and 220Rn activity concentration and the highest
radiation dose due to these radionuclides (Table 2), as expected,
validating the results of these calculations. Therefore, all analyzed
water sources do not offer health risk in terms of 222Rn and 220Rn
ingestion, according to the dosimetric levels reported in this paper.
5. Conclusion
This study reported a comparative evaluation of the radioac-
tivity due to 222Rn and 220Rn in several well-known Brazilian
mineral waters occurring at São Paulo and Minas Gerais states.
According to the Brazilian Code of Mineral Waters (BCMW)
guidelines, three temperature categories were defined for the
analyzed waters, i.e. cold (<25  C, 41 samples), hypothermal (25e
33  C, 33 samples) and mesothermal (33e36  C, 1 sample). The
investigation was held also monitoring the presence of the
following dissolved gases: O2, CO2 and H2S. An inverse relationship
was found between temperature and dissolved O2, indicating that
the increasing temperature causes a decrease in dissolved O2 of the
analyzed waters. A trend of inverse relationship between temper-
ature and dissolved CO2 was identified in the hypothermal and
mesothermal waters, also indicating that its solubility decreases
accompanying the temperature raising. According to the BCMW
guidelines, 33 water sources were carbogaseous (contained dis-
solved CO2 corresponding to a minimum of 200 mL per liter),
whereas 3 were sulfured waters (contained dissolved sulfide cor-
responding to a minimum of 1 mg/L). The 222Rn activity concen-
tration range was 0.02e112.5 Bq/L, whereas the 220Rn activity
concentration range was <4e895 mBq/L. The highest 222Rn levels
were found in Boi and Villela springs located at Águas da Prata city
(São Paulo State) and Dona Beja spring situated at Araxá city (Minas
Gerais State) that are sites characterized by the abundant presence
of natural radioelements in the rock matrices. A significant rela-
tionship was found between dissolved radon and thoron in the
hypothermal and mesothermal waters, perhaps related to tem-
perature effects on the dissolution of their parents 226Ra and 224Ra
from the rock surfaces. According to the BCMW guidelines, none of
the water sources were thoriferous (dissolved thoron lower than 2
Mache unit/L), whereas the waters of Vitória and Boi springs were
weakly radioactive (222Rn levels between 5 and 10 Mache unit/L)
and the waters of Villela and Dona Beja springs were radioactive
(222Rn levels between 10 and 50 Mache unit/L). The waters of Vil-
lela and Dona Beja springs exhibited 222Rn activity concentration
exceeding the WHO guidance level of 100 Bq/L in drinking-water
for public water supplies, as well the maximum a-energy intake
for radon progeny corresponding to 0.4  103 J that is about 100
times lower than the IAEA guideline reference value. The maximum
thoron progeny intake was 5  105 J for the geyser at Caxambu
city, Minas Gerais State, that is almost 2600 times lower than the
IAEA guideline value and circa 80 times lower than the maximum
a-energy intake for radon progeny at Villela and Dona Beja springs.
Thus, 220Rn doses were much lower than that of 222Rn and the
calculations in this paper indicated that all analyzed mineral waters
do not offer health risk in terms of these radionuclides ingestion as
the activity concentrations do not reach high enough values for
their decay products to produce significant doses.
Acknowledgments
FAPESP (Foundation Supporting Research in São Paulo State)
and CNPq (National Council for Scientific and Technologic
30 D.M. Bonotto / Journal of Environmental Radioactivity 132 (2014) 21e30
Development) in Brazil are greatly acknowledged for financial
support of this investigation. Two anonymous reviewers are
thanked very much for helpful comments that improved the
readability of the manuscript.
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