J. Environ.

Radioactivity,

Vol. 31 No. 1, pp. 21-28, 1996

Copyright 0 1996 Elsevier Science Limited

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0265-931X(95)00003-8

Study of Natural Radionuclides and Radon Emanation in

Bricks used in the Attica Region, Greece

A. Savidou, C. Raptis & P. Kritidis

Institute of Nuclear Technology-Radiation
Protection, National Centre for Scientific
Research Demokritos, Athens, Greece
(Received 12 July 1994; accepted 20 December 1994)

ABSTRACT
Bricks commonly used in the Attica region, Greece have been studied for
both natural radionuclide content and radon emanation. The high-resolution y-ray spectroscopy technique, as well as radon exhalation measurements, have been employed. For determination of radon exhalation rate,
besides the trivial method which consists of a single measurement of radon
concentration in a closed vessel containing the sample, a shorter duration
continuous accumulation/counting method has been established, The results
of radon exhalation measurements have been used together with the
y-spectrometry determination of 226Ra in order to determine radon emanation coefficients.

INTRODUCTION
A study of natural radionuclides and radon emanation in bricks used in
the Attica region has been initiated at our laboratory as a part of a
broader programme designed to characterise Greek building materials as
indoor radon sources.
An important parameter characterising the physical behaviour of radon
in materials is the emanation coefficient, the fraction of radon atoms that
escape from a mineral grain into the contiguous pore space. The knowledge of this parameter makes it possible to determine other features of a
material related to radon. For the determination of the emanation coeffi21

22

A. Savidou et al.

cient, a high-resolution y-spectrometry device and a method for determination of the radon exhalation rate are used in conjunction.
There are many experimental methods for the determination of the
exhalation rate. The mostly-used method is the closed vessel method
which is based on a single measurement of radon concentration in a closed
vessel containing the sample (Ingersoll, 1983; Jonassen, 1983; Bossus,
1984; Barton & Ziemer, 1986). The accumulation period of this method
extends to a few days. Another measurement technique is to allow gas
flow (air or nitrogen) through a container holding the sample or connected to the sample and to calculate the emanation parameters on the basis
of equilibrium level of Rn in the gas leaving the container (Stranden, 1979;
Poffijn et al., 1984; Dijk & Jong, 1991).
In the present work the closed vessel method has been used for the
determination of radon exhalation from bricks. The reason for this choice
is that only a small amount of material is needed for the measurements.
On the other hand, this method has the disadvantage that as the Rn
concentration in the vessel increases, the exhalation rate decreases due to
the reverse entry process. As suggested by Poffijn et al. (1984), the ratio of
the free vessel volume to the sample volume must exceed 10 in order to
consider the reverse effect as negligible.
In this study the ratio of the free vessel volume to the sample volume is
about 5. The small sampling volume results in a lower detection limit, but
the measurements may be affected by the reverse entry process to a certain
extent. For three brick samples which showed higher radon exhalation, a
short-time continuous accumulation/counting
method has been performed
as well. The accumulation period of the accumulation/counting
method is
shorter (only a few hours are needed to determine the exhalation rate of a
typical sample). This results in reduced influence of the back diffusion.

MATERIALS

AND METHODS

Brick samples have been collected from major local producers, representing 80% of the total production in Attica.
Measurements of the specific activities in bricks

The specific activities of 226Ra, 232Th and 40K have been determined by
use of high-resolution y-spectrometry. The samples are powdered, closed
in 75cm3 sealed containers and kept about 3 weeks before measurement
in order to achieve radioactive equilibrium between 226Ra, radon and its
short-lived decay products. The concentration of 226Ra is derived from

Natural radionuclides and radon emanation in bricks

23

the 295 keV and 352 keV photopeaks of 214Pb and the 609 keV photopeak of 24Bi as the mean value. The 186 keV photopeak of 226Ra is not
used because of the interfering peak of 235U, with energy of 185.7 keV.
The 232Th concentration is determined from the 583 keV and 911 keV
photopeaks of 208T1 and 228A~, respectively. The 40K concentration is
determined from its 1460 keV photopeak. The counting time is 12 000 s.
Measurements

of the radon exhalation rate

For these measurements the samples are crushed into pieces smaller than
1 cm in order to ensure that all radon that enters the contiguous pore
space of the sample emanates into the chamber. An amount of about 300 g
of sample is used for each measurement.

(4 Closed vessel method

The closed vessel method has been used to measure the radon exhalation
rate of the samples. The volume of the accumulation chamber is 1.2 litres;
(Fig. 1). When the samples are sealed in it, the available vessel volume is
about 1 1. Silicon High Vacuum grease is used to ensure sealing. After a
given sealing time (20, 70 or 96 h), an amount of air is transferred from
the accumulation chamber to a scintillation chamber by 10 min circulation that ensures uniform mixing. A filter is used to isolate the radon
progeny. The a-activity in the scintillation chamber is counted after 3 h to
allow for the equilibrium between radon and its daughters to be established.
The system has been calibrated by use of a thin 226Ra standard with
negligible back diffusion. The background of the detector is typically
below 2cpm and the efficiency for detection of the a-particles of radon
and its daughters is about 90%. The comparison between the theoretical

Air pump

Filter

Chamber

Fig. 1. Schematic

diagram

of the closed vessel method.

24

A. Savidou et al.

and the experimental data for radon decay confirms

leakage from the accumulation chamber. Measurements
made during several hours of circulation of air with
concentration. The results have shown that there is no
circulation.

the absence of
have also been
constant radon
leakage during

(b) Continuous accumulation/counting method

The measuring system is the same as in the case of the closed vessel
method, but the air is circulating continuously and the counting is
continuous as well. The concentration of radon and its daughters in the
scintillation chamber increases with time. The accumulating counts are
proportional to the time integral of the total a-activity in the chamber. A
thin 226Ra standard is used for calibration. The advantage of the method
is the shorter accumulation period (a few hours), which results in reduced
influence of the back diffusion process. The monitoring of the back
diffusion process is possible by comparing the experimental data with
those derived by use of a thin 226Ra standard. When the back diffusion is
negligible, the ratio of sample counts to the standard source counts after a
certain period of time is given by the formula

c SPl
-=
C SK

Bspl. Qspl
&c . Qsrc

(1)

where C,,,, C,,,: the counts after sample and source measurement; Bspl,B,,,:
the ratio of the scintilation chamber volume to the available vessel volume
for the sample and the source, respectively; and Qspl, Qsrc the emanation
rates of the sample and source.
The first experimental results for bricks indicated a significant
presence of thoron in the measuring chamber. The half-life of thoron is
55.6 s, while that of radon is 3.8 days. When a brick sample is measured,
the a-count integral is linear with time in contrast with the calibration
curve obtained with the thin 226Ra source. This indicates that the
number of a-decay nuclei in the vessel remains stable. Due to its low
half-life, the thoron concentration in the vessel is stable within a few
minutes after sealing. So the a-count integral linearity seems to be related to thoron. The double counts which have also been observed during
these measurements confirm the presence of thoron. The double counts
result from 220Rn and its first progeny 216Po which has O-15 s half-life.
To prevent the counting of thoron, the samples were put in a pot and
covered hermetically with a thin plastic membrane (PVC). No double
count was detected after this sample treatment. The number of double
and single counts accumulated during a half-hour circulation through a

25

Natural radionuclides and radon emanation in bricks

TABLE 1
Accumulating
Counts during a Half-Hour
Circulation through a Chamber Containing a
Brick Sample Immediately after Closure

Without membrane
With membrane

Total

Double

Single

31
26

5
0

21
26

chamber containing a brick sample with and without the plastic

membrane are shown in Table 1. The circulation starts immediately after
the sample sealing.
The plastic membrane does not prevent the diffusion of radon. The radon
accumulated in the sampling vessel before and after covering the radon
source is the same, while the cc-count integration curve after covering the
sample with the membrane is similar to that of the source. The integral of c(counts as a function of time in the case of the continuous accumulation/
counting measurements is shown in Fig. 2, including the calibration curve,
those of a radium-rich mineral and a brick sample without the plastic cover
as well as the theoretical curve calculated for the thin radium source.
In this study only three brick samples, characterised with higher exhalation rates, have been measured by use of the continuous accumulation/
counting method. The results were consistent with those of the closed
vessel method.
0

4000
r

50

100

150

Them.

200

250

300

T (min)

Fig. 2. The integral of cc-counts as a function of time in the case of the continuous
accumulation/counting
measurements,
including the calibration
curve, those of a
radium-rich mineral and a brick sample without the plastic cover as well as the theoretical curve: theoretical curve; 0 brick; H mineral; [7 source.

26

A. Savidou et al.

RESULTS AND DISCUSSION

The average values of the radium, thorium and potassium specific activities, together with the average specific exhalation rate and the average
emanation coefficient of radon are given in Table 2. The barometric
pressure, temperature, and humidity (50%) were those of the air-conditioned laboratory building. Similar results for bricks from some other
countries are given also in Table 2 for comparison. Since the units in
which the exhalation rate is expressed vary from one publication to
another, the results have been converted as necessary. The natural radionuclide contents in bricks used in Attica agree well with the values found
by other groups. The average radon emanation coefficient is in the range

Radon

Emanation

TABLE 2
Rates and Radionuclide
Content

in Bricks from Different

Specific activities (Bq kg-)

This study
Range
Average
SD
Netherlands (2 samples) a
1
2
Belgiumb
Range
California
Average
New Mexico
Average
Australiad
Average
Finland (clay brick)
Range
Average
Finland (white brick) e
Range
Average

Studies

226Ra

232Th

40K

Radon specfic
exhalation rate
(Bq kg- h-l)

25-83
35.6
12

35-65
51.5
8.9

539-1058
732
158

0~0013-0~035
0.008
0.009

0.5-12.4
2.8
3.2

0.0034

1.2
0.7

39.1
75.5

Emanation
coefjcien t
(%)

0.1-2.2

41

89

681

37.1-I 34
79.8

37.5-91.7
61-6

780-1185
986

19.9925 1
23

14.5-28.8
21

537-699
622

ODijk and Jong (1991).

bPoflijn et al. (1984).
Ingersoll (1983).
d Beretka and Mathew (1985).
e Mustonen (1984).

0.0037

0.013

Natural radionuclides and radon emanation in bricks

Measurements

of Radon

TABLE 3
Specific Exhalation

Closed vessel method

1
2
3

21

Rates in Bq kg- h-

Accumulation/counting

method

20 h sealing

96 h sealing

8 h circulation

7 h circulation

6 h circulation

0.031 zt 0.005

0.029 * 0.003
0.035 It 0.003
0.012 f 0.002

0.032 zt 0.006
0.042 St 0.006
0.015 f 0.004

0.03 1 zt 0.006
0.042 & 0.006

0.040 zt 0.01

of values measured in other countries, although some values determined in

this study are a little higher.
The results for the samples analysed by use of both methods are
presented in Table 3. The two methods appear to be in good agreement.
The repeatability of both methods has been checked by replicate
measurements of the standard source. Five measurements have been taken
for each time interval of sealing and for the continuous accumulation/
counting method. The results show that the total relative error of the
methods is lower than 15%.
The low detection limits (3 0 of the background) of the trivial method
and continuous accumulation/counting
method are shown in Table 4.

CONCLUSIONS
The experimental data show large variations of the emanation coefficients
in bricks. Therefore, the radium content alone cannot be used to evaluate
the exhalation rate of radon from bricks.
Since the results of a few hours radon accumulation are consistent with
those of some days accumulation we can conclude that the back diffusion
process is not significant in our measurements.
The proposed continuous accumulating/counting
method is an accurate
TABLE 4
The Detection Limits
Closed vessel method
Sealing
time (h)
20
70
96

Radon exhalation
rate (IO-' Bqh-)
2
0.7
0.6

Accumulation/counting

method

Circulation
period (h)

Radon exhalation
rate (lo- Bq hF)

6
7
8

9
7.2
6

28

A. Savidou

et al.

and fast technique for determining the specific radon emanation rate. This
method is planned to be used for determination of the exhalation rate of
radon from concrete. Only a few hours of circulation are sufficient to
determine the exhalation rate of a typical concrete sample.

ACKNOWLEDGEMENT
The present work has been financially supported by the European Union in
the frame of Project F13P-CT92-0061 of the EU Radiation Protection
Action.

REFERENCES
Barton, T. P. & Ziemer, P. L. (1986). The effects of particle size and moisture
content on the emanation of Rn from coal ash. Health Phys., 50, 581-8.
Beretka, A. J. & Mathew, P. J. (1985). Natural radioactivity of Australian building materials, industrial wastes and by-products. Health Phys., 48, 87-95.
BOSSUS,D. A. W. (1984). Emanating power and specific surface area, Radiat.
Prot. Dosim., 7, 73-6.
Dijk, W. & Jong, P. (1991). Determining the Rn exhalation rate of building
materials using liquid scintillation counting. Health Phys., 61, 501-9.
Ingersoll, J. G. (1983). A survey of radionuclide contents and radon emanation
rates in building materials used in the US. Health Phys., 45, 363-8.
Jonassen, N. (1983). The determination of radon exhalation rates. Health Phys.,
45, 363-8.
Mustonen, R. (1984). Natural radioactivity in and radon exhalation from Finnish
building materials. Health Phys., 46, 1195-203.
Poffijn, A., Bourgoignie, R., Marijns, R., Uyttenhove, J., Janssens, A. & Jacobs,
R. (1984). Laboratory measurements of radon exhalation and diffusion.
Radiat. Prot. Dosim., 7, 77-9.
Standen, E. (1979). A simple method for measuring the radon diffusion coefficient and exhalation rate from building materials. Health Phys., 37, 242-4.