DOI: 10.1007/s10967-007-7326-0 Journal of Radioanalytical and Nuclear Chemistry, Vol. 279, No.

2 (2009) 487491
02365731/USD 20.00 Akadmiai Kiad, Budapest
2008 Akadmiai Kiad, Budapest Springer, Dordrecht

Radium-226 concentration in Romanian bottled mineral waters
M. Moldovan,
1
* C. Cosma,
1
I. Encian,
2
T. Dicu
1

1
Babes-Bolyai University, Faculty of Environmental Science, 4, Stefan cel Mare, Cluj-Napoca, 400192, Romania
2
CNCAN National Committee for Nuclear Activities Control, Bucharest, Romania
(Received April 11, 2008)
Radium concentration was determined in 23 types of bottled mineral waters, commercially available in Romania. Using the Lucas cells with the
device Luk 3A, the radium concentration was determined directly, after the radon balanced with radium. From these measurements, the
corresponding annual effective ingestion dose was determined.
Introduction
The occurrence of natural radionuclides from
238
U
and
232
Th series in drinking water has been the subject
of extensive studies. Most of these studies were
concerned with the drinking water standards for gross-
alpha activity and Ra, established by the Environmental
Protection Agency,
1
and World Health Organization.
2
These studies have been performed mostly for the
assessment of the dose and the risk that results from
drinking this type of water.
Radium-226 and its daughter products are
responsible for a major fraction of the internal dose
received by humans from naturally occurring
radionuclides. It has long been known also that many
mineral springs contain relatively high concentrations of
radium and radon.
Published values of
226
Ra in mineral waters ranged
to more than 3.7 Bq
.
L
1
(100 pCi
.
L
1
), several times
greater than values normally reported for public water
supplies.
3

Recent national and international regulations on
water intended for human consumption expressly
exclude bottled mineral waters.
4
Bottled mineral waters
have always been regarded as a voluptuary good,
something between a soft drink and a dietary or medical
aid with a limited importance in human diet. Nowadays
the consumption of bottled mineral waters has become
very popular. A considerable segment of the population
drinks almost only mineral water as drinking water,
which is about 1 L
.
d
1
. As is known, some kinds of
mineral waters contain naturally occurring radionuclides
in higher concentration than the usual drinking water.
In the last years, consumption of bottled mineral
water has widely increased in all countries also in
Romania. The average individual consumption of
bottled mineral water is 0.36 L
.
d
1
in Europe.
For example, in the period 19902000, mineral water
consumption increased of 50% in Germany and of 130%
in U.S.A. At present, about 9,000 million liters are

* E-mail: mmircea@enviro.ubbcluj.ro
yearly sold in Italy, the average individual consumption
is 160 L/year.
5
The Brazilian production of bottled
mineral water is about 1.8
.
10
9
L
.
year
1
.
6
In Hungary
the average consumption of mineral water was
28 L
.
person
1.
year
1
in 1999, while in 2000 this amount
reached nearly 40 L
.
person
1.
year
1
. According to the
surveys, the 2059 year old age group is the most
important consumer of the mineral water, and about
18% of this group drinks mineral water every day.
7

The consumption of bottled mineral waters has
recently become more popular in Romania. The rate of
consumption increased nearly seven times from 1989 to
2000. The average consumption of mineral water was
28 L
.
person
1.
year
1
in 1999, while in 2006 this amount
reached nearly 50 L
.
person
1.
year
1
.
8

Due to a higher standard of living, a certain group of
the population fulfils its need for drinking water almost
exclusively with bottled mineral water. The
consumption varies around 1 L
.
person
1.
day
1
. It has
been determined in many cases, in different countries,
that the
226
Ra concentration in mineral water is higher
than that in tap water.
911
The enrichment of radium in
drinking water and food enhances the ingestion dose due
to its long physical and biological half-life.
The elevated ingestion of
226
Ra might provide an
annual internal dose near to 0.1 mSv
.
year
1
that is the
reference level recommended by the World Health
Organization.
1
Therefore, the determination of the
concentration of
226
Ra in mineral water has become
important.
The
226
Ra concentrations of the bottled mineral
waters commercially available in Romania were
measured using the Lucas cell method. After the
measuring sequence, samples with different bottling
times (20062007) were investigated from those types
of mineral water that showed
226
Ra concentration higher
than 100 mBq
.
L
1
. Based on the average concentration
values and in the case of a regular consumer (1 L
.
day
1
),
internal doses were estimated that could be attributed to
the consumption of those types of water.
M. MOLDOVAN et al.: RADIUM-226 CONCENTRATION IN ROMANIAN BOTTLED MINERAL WATERS
488
Methods of measurement and assessments
Generally,
226
Ra, the direct forerunner of radon, is in
secular equilibrium with the last one. We note with
Ra

and
Rn
the decay constant of radium and radon,
respectively, and with N
Ra
and N
Rn
the number of atoms
of radium and radon, respectively. In the case of secular
equilibrium, for a time t<<T
1/2
(Ra), where
T
1/2
(Ra) = 1620 years, the parent radium desintegration
speed is actually constant, therefore, we can
approximate 1
t
Ra
e

, meaning N
Ra
= N
Ra
(0) and the
number of radon atoms is given by:
) 1 (
t
Rn
Ra
Ra Rn
Rn
e N N

(1)
Moreover, if tT
1/2
(Rn), where T
1/2
(Rn) = 3.82 days,
then 0
t
Rn
e

, which leads to

Rn
Ra
Ra Rn
N N

= (2)
or
Rn
.
N
Rn
=
Ra
.
N
Ra
, which means that the activities of
the parent (
226
Ra) and the daughter (
222
Rn) become
equal.
The radon concentration is equal to the radium
concentration, this happens after a period of 30 days
when radium can be considered in secular equilibrium
with radon. In all the used calculations we will refer to
radon concentration measurement which is actually the
activity concentration of radium.
The radon in water was measured using a LUK-3A
device
12,13
specially adapted for radon in water
measurement. This equipment called LUK-VR consists
of a 500 mL scrubber where a known quantity of water
(300 mL) is introduced (Fig. 1). Before measuring, the
water was tempered to room temperature.



Fig. 1. The scheme of the LUK-VR device


After one minute of strong shaking, the equilibrium
(depending on the temperature) between the radon in
water and radon in the air above the liquid is established.
Coupling a Lucas cell previously emptied to scrubber
using a stopcock and also a Janet syringe containing
150 mL of pure water and then opening this stopcock
the air containing radon is transferred from scrubber into
the Lucas cell (145 mL). The radon progeny is kept
before entry into cell by a filter inserted between
scrubber and Lucas cell. The detection efficiency is
1.46 counts/Bq for a delay time of 15 minutes between
cell filling and the start of measurement (PLCH
constant).
12
We used an efficiency constant of 1.24,
determined by a 5-minute measurement which started 2
M. MOLDOVAN et al.: RADIUM-226 CONCENTRATION IN ROMANIAN BOTTLED MINERAL WATERS
489
minutes after the transfer. This constant was found using
a standard RaCl
2
solution (STANDARD 12051 AER,
Romania). The diminishing of the delay time was
necessary to increase the number of samples analyzed
per hour. Considering all the time periods (scrubber
operation, empty Lucas cell, filling Janet syringe, delay
and measure) about 14 minutes were necessary,
therefore, 4 samples per hour could be examined. The
measuring of Lucas cells activity was made by direct
coupling of these cells to the photomultiplier included in
LUK-3A device. For a room temperature of 20 C, the
solubility coefficient of radon in water is 0.254 and for
other working temperatures the following equation was
used:
14,15

= 0.105+0.405 exp (0.0502
.
t) (3)
where t is the water temperature (C) in the scrubber.
Between the radon content in water A(Bq/L) and the
number of counts/second N(c/s) there is the following
relation:
19

A(Bq/L) = 9.85 N(c/s) (4)
A volume of two liters of water was evaporated to
obtain 0.5 L, which was enclosed for a month in glass
bottles well sealed. The radon in equilibrium with
radium was measured as above. Considering all types of
errors (statistic, measurements) of about 25%, for the
radium water content measurement, in this way the
detection limit was turned down to 0.05 Bq/L for
radium. The efficiency of the Lucas cell was determined
using the control source, that was manufactured and
attested by The State Metrological Institute of the Czech
Republic.
In the case of a 1 L
.
day
1
consumption rate of
mineral water, the committed effective dose assessments
were provided by the activity of the annually ingested
226
Ra multiplied by the proper dose conversion factor.
In our calculations the dose conversion factors shown in
Table 1 were used.
Results and discussion
The radium concentration was determined for 23
kinds of bottled mineral waters available in Romania.
The distribution of
226
Ra concentration in the different
types of bottled mineral water is shown in Fig. 2.

Table 1. Dose conversion factors
WHO
3
Adults 2.2
.
10
7
Sv
.
Bq
1

IAEA
16
27 years old
712 years old
1217 years old
Adults
6.2
.
10
7
Sv
.
Bq
1

8.0
.
10
7
Sv
.
Bq
1
1.5
.
10
6
Sv
.
Bq
1

2.8
.
10
7
Sv
.
Bq
1


Table 2. Radium concentration in bottled mineral waters
Concentration of
226
Ra, mBq
.
L
1

Type of water
(number of samples)
Average

Minimum

Maximum

Standard
deviation
Median
A (5) 132.8 108 156 18.4 132
B (5) 116.8 100 136 14.8 120
C (5) 119.2 116 104 12.7 116
D (2) 84 80 88 5.6 86
E (3) 130.6 116 148 16.1 128
F (3) 198.4 172 228 21 196
G (3) 440.8 404 476 33.1 440
H (4) 84 60 96 16.3 90
I (3) 185.3 168 208 20.5 180
J (3) 158.6 148 172 12.2 156
K (3) 61.3 52 72 10 60
L (3) 77.3 60 88 15.1 84
M (3) 62.6 56 68 6.1 64
N (5) 443.2 360 488 49.5 452
P (3) 69.3 64 76 6.1 68
Q (3) 96 92 100 4 96
R (3) 94.6 88 100 6.1 96
T (3) 277.3 252 296 22.7 284
U (3) 349.3 332 368 18 348
W (3) 78.6 72 84 6.1 80
V (2) 62 60 64 2.8 61
Y (3) <LD
Z (3) <LD
LD: Limit of detection.

M. MOLDOVAN et al.: RADIUM-226 CONCENTRATION IN ROMANIAN BOTTLED MINERAL WATERS
490

Fig. 2. The distribution of
226
Ra concentration in the different types of bottled mineral water

Table 3. The estimated committed effective dose of different age groups of radium from drinking
1 L
.
day
1
of bottled mineral water using the ingestion dose conversion coefficients from the IAEA (1995)
and WHO (1993)
Annual committed effective dose, mSv
IAEA (1995) WHO (1993)
Type of water
27 years old 712 years old 1217 years old Adults Adults
A 0.030 0.038 0.072 0.013 0.010
B 0.026 0.034 0.064 0.011 0.009
C 0.027 0.035 0.065 0.012 0.009
E 0.030 0.038 0.071 0.013 0.01
F 0.045 0.058 0.108 0.020 0.015
G 0.100 0.128 0.241 0.045 0.035
I 0.041 0.054 0.101 0.018 0.014
J 0.035 0.046 0.087 0.016 0.012
N 0.100 0.129 0.242 0.045 0.035
T 0.062 0.080 0.151 0.028 0.022
U 0.078 0.101 0.191 0.035 0.028


In twelve cases the
226
Ra concentration is less than
100 mBq
.
L
1
, value that is characteristic for the mineral
drinking waters in Romania.
17,18
In eleven samples the
226
Ra concentration is more than 100 mBq
.
L
1
. Table 2
contains the types of mineral water with the radium
concentration. In all cases the
226
Ra concentration is less
than 500 mBq
.
L
1
.
Reapeted measurement of the same type of mineral
water sample have shown variation less than that of the
total errors (25%).
In Romania the water consumption has increased up
to 50 L a year for a person. There are four big producers
that own 55% of the production and distribution of
bottled mineral water. They are: A Borsec with 20%, F
European Drinks with 17%, R Dorna with 10% and
D Perla Harghitei with 8%.
As one can notice from the table, only two types of
water belonging to big producers have a radium
concentration over 100 mBq
.
L
1
.
Table 3 contains the calculated annual effective dose
coming from the radium for various age groups,
assuming a daily consumption of 1 L
.
day
1
of types of
mineral water (Table 2), with higher than 100 mBq
.
L
1

226
Ra concentration. Different consumption rates of
mineral water cause proportionately different doses. In
several countries the
226
Ra concentration in drinking
water is limited to 100 mBq
.
L
1
.
According to a former WHO directive a limit of
100 mBq
.
l
1

226
Ra concentration was recommended.
This was changed in the newest issue of the WHO
recommendation,
1
where the suggested annual
committed effective dose caused by water consumption
M. MOLDOVAN et al.: RADIUM-226 CONCENTRATION IN ROMANIAN BOTTLED MINERAL WATERS
491
is less than 0.1 mSv. The latter value is recommended
by the European Union (Council Directive 98/83/EC,
1998). Using the dose conversion factors from standards
of the International Atomic Energy Agency (IAEA) it
equals to 489 mBq
.
L
1
with a 2 L
.
day
1
water
consumption for adults. In the case of the age group
(1217 years), the value of 0.1 mSv results in
91 mBq
.
l
1
radium concentration.
The
226
Ra average activity concentration measured
in Romania bottled mineral waters presented in this
paper (155.7 mBq
.
L
1
) is similar to those determined by
BOMBEN et al.
19
in bottled mineral waters from
Argentina (180 mBq
.
L
1
). Another study was recently
performed by SANCHEZ et al.
20
who determined the
radioactivity concentrations in 43 samples of bottled
mineral waters consumed in France, Portugal and Spain
the corresponding
226
Ra concentration activities varied
from 60 to 1.860 mBq
.
L
1
. OLIVEIRA et al.
6
obtained
similar average activity concentrations of
226
Ra in the
35 samples of bottled mineral water analyzed in Brazilia
with arithmetic mean activities ranged from 2.2 to
647 mBq
.
L
1
.
Considering the above average value for Romanian
water, the corresponding total committed effective dose
obtained is 6.7
.
10
2
mSv
.
y
1
. This value represents less
than 2.8% of the average effective dose attributable
annually from natural background radiation. Collective
dose due to the consumption of these waters was
evaluated to 66 manSv. For this calculation it was
considered that the Romanian production of bottled
mineral water is about 1.1
.
10
9
L
.
year
1
.

Conclusions
In recent years the consumption of mineral water in
Romania has increased to a great extent. In the majority
(52%) of mineral waters the
226
Ra concentration did not
exceeded the 100 mBq
.
l
1
value.
According to the results of this study, it is evident
that the activity concentration of radium measured in
mineral water in the assumed ratio presents no
significant risk for the Romanian population. The
concentrations and the effective doses due to intake of
226
Ra in mineral drinking water are compared to
the findings of similar works in other parts of the
world.
2123

The expected doses from consumption of mineral
water in Romania are insignificant compared with other
natural sources of radiation (such as radon in indoor air,
40
K, etc.).
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