ARTICLE IN PRESS

Applied Radiation and Isotopes 66 (2008) 215–222

www.elsevier.com/locate/apradiso

Radioactivity and Radiation Measurements

A comparison of alpha and gamma spectrometry for environmental

natural radioactivity surveys
Saı̈doua,b, Franc- ois Bochuda, Jean-Pascal Laedermanna,
M.G. Kwato Njockb, Pascal Froidevauxa,
a
University Institute of Applied Radiophysics, University of Lausanne, Grand-Pré 1, 1007 Lausanne, Switzerland
b
Centre for Atomic Molecular Physics and Quantum Optics, University of Douala, P.O. Box 8580, Douala, Cameroon
Received 23 August 2006; received in revised form 16 April 2007; accepted 6 July 2007

Abstract

An a-spectrometry, using automated borate fusion and sequential extraction and exchange chromatography, was used to determine
the uranium and thorium based on environmental radioactivity of 20 soil samples. The same set of the samples was analysed using
g-spectrometry with an HPGe detector. The two data sets were checked for coherence using Z-score and w2 statistical tests. We show that
g-spectrometry is a valid alternative to time-consuming a-spectrometry for the determination of natural uranium and thorium activity in
soil (activity range: 12.5–58.2 Bq/kg). The measured activities were compared with the theoretical activities to ensure secular equilibrium
in the 238U and 232Th series. For 226Ra, a special study was made on deconvolution of the 186 keV multiplet with the
Levenberg–Marquardt algorithm. Finally, the combined use of Z-score and w2-tests was found to be a powerful tool for comparing
the results obtained with two different methods.
r 2007 Elsevier Ltd. All rights reserved.

Keywords: g-ray spectrometry; a-particle spectrometry; Levenberg–Marquardt algorithm; Multiplet deconvolution; Z-score; w2-tests

1. Introduction is limited by the weak emission probabilities of many

Dose assessment from environmental radioactivity is
challenging because of the complicated absorption chain
from the environment to man. Naturally occurring radio-
nuclides are unevenly distributed in the earth’s crust, and
different transfer mechanisms from soil to plant, plant
to animal or man, and animal to man exist for
different nuclides in the natural 238U, 235U and 232Th
series. Environmental radiation surveys and dose assess-
ment programmes require rapid determination of radio-
nuclides, but there are numerous experimental and
metrological difficulties.
g-Spectrometry is a useful non-destructive method that
permits the simultaneous determination of many radio-
nuclides in a bulk sample, without the need for complicated
and time-consuming radiochemical separation. However, it
Corresponding author. Tel.: +41 21 623 34 80; fax: +41 21 623 34 35.
E-mail address: pascal.froidevaux@chuv.ch (P. Froidevaux).
potentially useful emission lines, the poor efficiency of
HPGe detectors over a wide energy range, the difficult task
of precisely calibrating the efficiency of the detector, and
the need to evaluate self-absorption and summation factors
(Garcia-Talavera, 2003; Yücel et al., 1998; Huy and Luyen,
2004).
a-Spectrometry, with a detection limit often 100–1000
times lower than g-spectrometry, is a very sensitive alternative
technique. The efficiency of a-particle detection depends only
on geometric factors and, when a careful radiochemical
separation process is carried out, it does not suffer from
spectral interference. However, the overall process is time-
consuming and impractical for large-scale screening of
environmental samples. In addition, radioactive tracers not
present in the environment must be used to accurately assess
activity—a requirement that is not always fulfilled. Thus,
a-spectrometry is used only for very specific aspects of
environmental radioactivity surveys, in particular for pluto-
nium determination, for which no other simple method exists.

0969-8043/$ - see front matter r 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apradiso.2007.07.034
 ARTICLE IN PRESS
216 Saı¨dou et al. / Applied Radiation and Isotopes 66 (2008) 215–222
In this work we describe a method, kept as simple as
possible, for the a-spectrometry analysis of thorium and
uranium isotopes in soil samples. We used a- and
g-spectrometry to determine the radionuclide content of
20 soils samples from a region in Cameroon with suspected
uranium ore deposits (Gehnes and Thoste, 1981; Oesterlen,
1985). The results were compared using Z-score and w2
statistical tests. The 238U and 232Th activities determined
by a-spectrometry were compared to the activities deter-
mined by g-spectrometry through 234Th and 228Ac or 212Bi,
respectively. Direct measurements of 226Ra through its
186.2 keV g-line were corrected by removing the 235U
contribution (185.7 keV) that was determined by a-spectro-
metry. The corrected direct measurements were compared
with g-spectrometry determination of 226Ra based on the
daughter products 214Pb and 214Bi. The latter technique
assumes secular equilibrium. The validity of this hypothesis
for these soil samples was checked by comparing the
experimental results with the theoretical values for 238U
and 232Th series. Finally, the Levenberg–Marquardt
algorithm was used to deconvolve the 186 keV multiplet
and the results were compared with the 235U and 226Ra
activities determined by experiment. The aim of this work
is to demonstrate, through a statistical analysis of data
from the two methods, that g-spectrometry is a valid
method to determine uranium and thorium series in soil
samples when large-scale screening is required, for example
in determining the impact of uranium ore deposits on a
specific population.
2. c-Line analysis
Direct measurement of 238U by g-spectrometry through
its line at 49.5 keV (0.084% emission probability) is very
difficult. However, if its daughter products are in secular
equilibrium, 238U can be determined from the 63.3 keV
(4.5% emission probability) g-ray and the 92.6 keV doublet
(92.4+92.8 keV; 2.6+2.6% emission probability) of 234Th
and the g-rays of 234mPa at 766.4 keV (0.21% emission
probability) and 1001.0 keV (0.83% emission probability)
(Garcia-Talavera, 2003).
The main advantage of 234Th and 234mPa are their short
half-lives (T1/2 ¼ 24.1 d for 234Th and T1/2 ¼ 1.17 min for
234m
Pa), which imply that secular equilibrium is reached 6
months after sampling for 234Th and around 10 min for
234m
Pa relatively to 234Th. Unfortunately, the 766.4 keV of
234m
Pa is a weak intensity line that can interfere with the
768.3 keV (4.8% emission probability) of 214Bi. In environ-
mental samples, the 1001.0 keV is also a weak intensity line,
and although it is the least affected by the self-absorption
effect, the weak intensity combines with the lower efficiency
of HPGe detectors at higher energies to give activities with
significant uncertainties (Yücel et al., 1998; Huy and
Luyen, 2004).
The 92.6 keV doublet coincides with the 93 keV peak of
the thorium (K) X-ray and 93.3 keV of 235U (4.5%
emission probability). So for samples with a high uranium
and thorium content, the 93 keV peak does not give an
accurate indication of 238U. At 63.3 keV, there is another
interesting 234Th line that includes contributions from the
63.9 keV (0.255%), 63.9 keV (0.023%) and 62.9 keV
(0.018%) emissions from 232Th, 231Th and 234Th, respec-
tively. In natural uranium and thorium samples, the
interference from 63.3 keV can be neglected (Yücel et al.,
1998).
The only method for direct measurement of 226Ra by
g-spectrometry is to use the single exploitable line at
186.2 keV (3.53% emission probability). However, there is
interference from the 186.05 keV (0.009% emission prob-
ability) of 230Th, 186.15 keV (1.76% emission probability)
of 234Pa, and 185.7 keV (57.2% emission probability) of
235
U (Wong et al., 2001). Because of the low branching
ratio for 234Pa, the contribution of the two first radio-
nuclides can be ignored. The most important interference is
from 235U, which has other exploitable lines at 143.7 keV
(10.9% emission probability), 163.3 keV (5% emission
probability) and 205.3 keV (5% emission probability).
Given that the activity of 235U in most soil samples is
low, it is best determined by a-spectrometry (Dowdall
et al., 2004; Karangelos et al., 2004). The 226Ra activity can
be deduced from the 186 keV multiplet after removal of the
235
U contribution. Alternatively, 226Ra can be determined
from the emissions of its daughter nuclides 214Pb and 214Bi,
following a period during which the sample has been
hermetically sealed to ensure secular equilibrium between
226
Ra and its progeny by avoiding gaseous 222Rn to escape
(Karangelos et al., 2004).
For 232Th, the only exploitable line at 59 keV (0.15%
emission probability) has a very weak intensity in environ-
mental samples. Thus, it must be determined from the
emissions of its daughter nuclides 228Ac, 212Pb or 212Bi.
3. Experimental method
3.1. Sampling
Twenty soil samples from suspected uranous areas of
North Cameroon in central Africa were collected, dried,
sieved (2 mm) and homogenised. For the measurements,
the samples were filled in a cylindrical 500 ml Semadeni
container (+ ¼ 9.5 cm, height ¼ 8 cm) and sealed with
paraffin for 1–2 months before counting to re-establish the
radioactive equilibrium between 226Ra and its daughter
products due to the possible escape of 222Rn during
handling (Righi et al., 2000).
3.2. g-Spectrometry
All measurements were performed with a Canberra
p-type HPGe well detector (GCW4523) with a total active
volume of 206 cm3, a relative photopeak efficiency of 45%,
and a resolution at 122 and 1332 keV of 1.24 and 1.93 keV,
respectively. The associated electronics consisted of a
 ARTICLE IN PRESS
Saı¨dou et al. / Applied Radiation and Isotopes 66 (2008) 215–222
Canberra preamplifier (model 2002CSL) and Accuspec
acquisition device. Treatment of the data was with the
GENIE 2000 program. The spectrometer was calibrated
using a liquid solution of 241Am, 109Cd, 57Co, 139Ce, 137Cs,
88
Y, and 60Co traceable to international standards and
emitting g-rays in the energy range 59–1836 keV. Coin-
cidence-summing corrections for 88Y and 60Co were
determined by Monte Carlo calculations (Décombaz
et al., 1992). The apparent full-energy-peak efficiency
(which would be obtained by neglecting the summing
effects) was calculated at the same time as the true one; the
ratio of these two values was the correction factor. The
self-absorption correction factors were also calculated by
Monte Carlo simulation (Bochud et al., 2006) whose
g-emissions were generated directly from the decay scheme
by the Sch2For code (Laedermann and Décombaz, 2000).
The correction was carried out line-by-line and the final
activity after correction for the given radionuclide was
estimated by
PN
Ai =u2i
A ¼ Pi¼1 N 2
, (1)
i¼1 1=ui
with the standard uncertainty given by
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1 IAEA-375: 238U (+20.5%), 234U (+20%), 226Ra
uA ¼ PN , (2)
i¼1 1=ui
2 (+4.5%), 232Th (+0.9%), 228Th (+3.8%); IRSN Inter-
where Ai is the activity calculated from the ith g-line, ui is
the standard uncertainty of the activity Ai, and N is the
number of identified g-lines for the radionuclide.
3.3. a-Spectrometry
For a-spectrometry, the dried and sieved soil samples
were ashed at 550 1C before dissolution and chemical
separation. In order to quantify the possible losses during
the whole separation process, a spike was added at the
beginning of the procedure (Rodriguez et al., 2001). We
used 232U (after removal of 228Th on an U/TEVA column)
and 229Th for uranium and thorium, respectively.
One gram of ashed sample was dispersed in a mixture of
LiBO2 (0.6 g), Li2B4O7 (2.4 g), and LiBr (15 mg) and
placed in a platinum crucible. The mixture was fused
on a Claisse M4 Fluxer (Claisse, 350 rue Franquet,
Sainte-Foy, Que., Canada), and then transferred from
the crucible to a Teflons beaker containing 50 ml of
water. Then 50 ml of HNO3 65% was added to yield an
8 M nitric acid solution (100 ml) to which 1 ml of
polyethylene glycol 2000 (0.2 M) was added to induce
flocculation (overnight) of boric acid and excess silicate
(Croudace et al., 1998). After filtration, the solution
was pumped (peristaltic Ismatec IPC-12) on an AG1x8
(10 ml) and Eichroms U/TEVA cartridges (2 ml)
stacked together. After washing with 60 ml HNO3 8 M,
the two columns were separated and thorium isotopes
eluted from the AG1x8 with 60 ml of HCl 32%. After
washing the resin with 10 ml of 9 M HCl, to remove
217
potential thorium contamination, uranium isotopes were
eluted from the U/TEVA cartridges with 20 ml of
0.01 M HCl. After evaporation, actinides were electro-
deposited from a buffered sulphate solution at pH 1.9, at
1.2 A over a period of 75 min using the method of Bajo and
Eikenberg (1999). With this method, overall yields are
usually above 80%.
The sources prepared by electrodeposition were counted
for a-particles using passivated implanted planar silicon
(PIPS) detectors with an active area of 450 mm2 in a
Canberra Alpha Analyst spectrometer. The source–detec-
tor distance was 5 mm for all measurements, giving an
efficiency of 25%. Standard sources of 241Am and 239Pu
were used for the energy and efficiency calibration of the
detectors.
3.4. Quality assurance
Quality assurance for the method developed in this work
was performed using IAEA reference materials IAEA-Soil-
6 and IAEA-375, as well as through participation in the
2005 intercomparison IRSN 77 SR 300 on the determina-
tion of natural radioactivity in a sample of lake sediments
(IRSN, 2005). Results—IAEA-Soil-6: 226Ra (+3.4%);
comparison 77 SR 300: 238U (5.7%), 234U (6.3%),
230
Th (5.4%), 226Ra (37.6%), 232Th (0%), 228Th
(+3.6%), 235U (4.1%). The values in parentheses are
the relative deviations from the reference values.
4. Activity and uncertainty calculations
4.1. g-Spectrometry
All activity determinations were made directly using
Genie 2000, except for the special case of 226Ra, where the
186 keV multiplet was corrected by removing the 235U
contribution determined by a-spectrometry. Thus, 226Ra
activity is given by
N 186  Að235 UÞmð235 UÞ186 mt
Að226 RaÞ ¼ , (3)
186 mð226 RaÞmt
where N186 is the total count for the 186 keV multiplet,
A(235U) is the activity of 235U in Bq/kg, m(235U)
and m(226Ra) are the emission probabilities of the 185.7
and 186.2 keV lines of 235U and 226Ra, respectively,
e186 is the detection efficiency of the 186 keV line, t is
the counting time in seconds, and m is the mass of the
sample in kg.
An effort was made to assess the comprehensive
uncertainty in accordance with international conventions
(ISO, 1995). After consideration, the contribution
of the counting time uncertainty was estimated to
be negligible, and the standard uncertainty in the
 ARTICLE IN PRESS
218 Saı¨dou et al. / Applied Radiation and Isotopes 66 (2008) 215–222

226
Ra activity is given by

DAð226 RaÞ
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u
u  2 "     226 2   #
u N 186 uN 186 2 u186 2 um ð RaÞ um 2
u 226
þ þ 226
þ
u 186 mð RaÞmt N 186 186 mð RaÞ m
u
¼u  2 " 235 2  226 2  235 2 # , ð4Þ
u
u mð235 UÞ 235 um ð UÞ um ð RaÞ uA ð UÞ
tþ 226
Að UÞ 235
þ 226
þ
mð RaÞ mð UÞ mð RaÞ Að235 UÞ

where ui is the standard uncertainty for the ith parameter. determination (Luca and Morel, 2004). After background
removal, the activity of a radionuclide in the sample
4.2. a-Spectrometry can be determined from the net peak area. The Total
Peak Area (TPA) method was used to assess the net count
The activity of a nuclide X was assessed as a function of (Shi et al., 2005; Gilmore and Hemingway, 2003). The
the spike activity of the nuclide Y. Neglecting the method is illustrated in Fig. 2. The net area of the peak is
uncertainty in the sample mass, the standard uncertainty given by
of the activity is given by !
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 2n þ 1 X
n X
n1 X
m
  N ¼GB¼ Ci  Ci þ Ci .
u2N ðXÞ þ u2b ðXÞ uA ðYÞ 2 u2N ðYÞ þ u2b ðYÞ 2ðm  nÞ
uA ðXÞ ¼ AðXÞ þ þ , i¼n i¼m i¼nþ1
N 2net ðXÞ AðYÞ N 2net ðYÞ
(6)
(5)
where, for the given a-line, b is the background level
expressed in number of counts, N is the raw number of
counts, and Nnet is the net number of counts (Nb).

5. De-convolution of the 186 keV multiplet by the

Levenberg–Marquardt algorithm

Direct determination of 235U and 226Ra by g-spectro-

metry was done using 185.7 and 186.2 keV, respectively. At
the resolution of the HPGe detector, these lines form a
multiplet at 186 keV that must be de-convolved before the
activity of each nuclide can be assessed. Note that the
following procedure might not be necessary with higher
resolution detector such as a Broad Energy Ge (BEGe)
detector. Fig. 1. De-convolution of the 186 keV multiplet by the Levenberg–Mar-
Non-linear least-square fitting techniques are currently quardt algorithm in two distinct peaks: 185.5 keV (235U) and 186.2 keV
used for similar computational problems to spectral de- (226Ra).
convolution. The Levenberg–Marquardt algorithm (Press
et al., 1992) is well suited for non-linear fitting, and was
used to de-convolve the 186 keV multiplet after the spectral
data was transferred from GENIE 2000 to the Origin
software (www.originlab.com). The centre and width of the
Gaussian peak were fixed using the peak width calibration
of the detector, and the peak height was left as a floating
parameter. The initial 226Ra height was set higher than
235
U in accordance with De Corte et al. (2005) and to the
theoretical value based on the constant ratio between 235U
and 238U activity in natural soil. This gave two distinct
Gaussian peaks corresponding to 235U and 226Ra (Fig. 1).
The estimation of background is important because it Fig. 2. Total Peak Area method (TPA). BL and BR are left and right
strongly influences the net area and associated uncertainty backgrounds, respectively. (2n+1) defines the number of channels in the
of the total absorption peaks, and hence the activity peaks region and (m–n) is the number of channels in BL and BR.
 ARTICLE IN PRESS
Saı¨dou et al. / Applied Radiation and Isotopes 66 (2008) 215–222 219

The standard uncertainty of N is given by Table 1

sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi g-Ray lines used to evaluate natural radioactivity in the soil samples
 
2n þ 1 2
sN ¼ G þ ðBL þ BRÞ, (7) Radionuclide Lines used (keV) Emission probability (%)
2ðm  nÞ
234
Th 63.3 4.5
where Ci is the number of counts for channel i, G is the 92.4 2.6
gross count, and B is the background. The left and right 92.8 2.6
backgrounds are BL and BR, respectively. The centre of 226
Ra 186.2 3.53
the peak is at the channel 0 position.
214
The number of channels in the peak region is (2n+1) Pb 295.2 18.5
352 35.8
and the number of channels in BL and BR is (m–n). The
214
ROI is centred on the peak with region B equal to 7s and Bi 609.3 44.8
each BL and BR equal to 1s, taking into account that the 1120.3 14.8
1764.5 15.4
FWHM ¼ 2.355s.
228
Ac 338.3 11.3
238 232 911.2 26.6
6. Theoretical estimation of the U and Th series
969 16.2
activity
212
Bi 727.2 6.65
1620.6 1.51
For a given mixture of radionuclides, the activities of the
progeny at any time can be calculated using the Bateman
formula or by a generalisation of the simple two-energy-
level decay formula activity of 12.5 Bq/kg and a maximum activity of
dN 57 Bq/kg for 238U. The 232Th activity was between 14.6
¼ lN, (8)
dt and 58.2 Bq/kg.
where l is the decay constant and N is the total number of Table 2 also presents the comparison of a- and
unstable nuclei at a given time t. The generalisation to a g-spectrometry by means of the Z-score for each radio-
decay chain of n energy levels is described by an nuclide. The fact that several values of |Z| are above the
n-dimensional vector N containing the number of nuclei threshold of |Z| ¼ 2 is not unusual since, even if the two
at each level and an n  n matrix K containing the distributions were in perfect agreement, 5% of the |Z|
probability transitions from one level to another. values would be expected to be above the threshold.
In a similar way to the two-level case, the temporal A simple test can be used to check the concordance of the
evolution is described by the equation two methods: if the Z-scores are normally distributed,
then the sum of the squared Z-scores should have
dN a w2 distribution. This translates into the following null
¼ KN, (9)
dt hypothesis:
which has the solution H0: There is no difference between a- and g-spectro-
metry. (Zi)i ¼ 1, y, n, where n is the number of degrees of
N ¼ eKt N 0 , (10)
freedom corresponding to the number of soil samples, is
where N0 is the vector number of radionuclides at an initial normally distributed and centred. The probability of a
time t0. type-I error is a ¼ 5% (Martin, 1971).
The exponential of the matrix was calculated using an ad If H0 is rejected, then a- and g-spectrometry are
hoc C-code program based on open source Lapack significantly different (a ¼ 5%), otherwise the two techni-
routines. The database for K matrices is JEF_2.2 from ques are considered to be statistically similar.
the web page of the OCDE Nuclear Energy Agency. Table 3 shows the results of the w2-test on the Z-score
values to test the H0 hypothesis. Activity determination by
7. Results and discussion a- and g-spectrometry are not significantly different (at the
5% level) in the three cases and 238U can be determined
Table 2 presents the two data sets for the 20 soil samples. through the g-analysis of 234Th, 232Th through 212Bi and
The first set contains the a-spectrometry results for 238U 226
Ra through 214Pb–214Bi. However 232Th determination
and 232Th, and the a/g-spectrometry results for 226Ra. The through g-spectrometry of 228Ac gives significantly differ-
second set contains the g-spectrometry results for 234Th, ent results compared to direct a-spectrometry. Thus,
228
Ac, 212Bi, and 214Pb–214Bi. In this work, the g-lines listed g-spectrometry of 232Th is measurable through 212Bi but
in Table 1 were used to evaluate the natural radioactivity of problematic through 228Ac.
the soil samples. The fact that our results show that a- and g-spectrometry
The environmental radioactivity screening results, for are not statistically different does not mean that they are in
the soil samples from the region with potential uranium all ways equivalent. This is particularly the case for the
deposits, showed normal soil activity with a minimum minimum detectable activity (MDA) which was estimated
 ARTICLE IN PRESS
220 Saı¨dou et al. / Applied Radiation and Isotopes 66 (2008) 215–222

Table 2
Activities (Bq/kg) and Z-score test results between a- and g-spectrometry activities for 20 soil samples
238
Sample Ua 234
Thb Zi Rac
226 214
Pb–214Bib Zi Tha
232 228
Acb Zi Tha
232 212
Bib Zi

1 12.5070.75 17.372.8 1.64 11.473.0 12.370.2 0.29 14.670.7 12.970.3 2.11 14.670.7 14.871.4 0.13
2 14.5070.85 15.373.0 0.24 10.473.8 12.470.2 0.54 15.470.7 12.670.3 3.59 15.470.7 16.471.4 0.65
3 13.470.7 14.873.0 0.46 10.874.0 11.570.2 0.18 15.170.7 14.070.3 1.47 15.170.7 11.371.3 2.57
4 12.870.6 13.272.8 0.14 13.273.7 12.270.2 0.26 16.870.6 16.070.3 1.08 16.870.6 17.371.3 0.36
5 25.471.3 19.874.1 1.3 12.273.3 13.170.2 0.27 16.370.6 16.470.4 0.06 16.370.6 17.771.3 0.96
6 34.071.4 36.177.4 0.27 22.573.8 20.070.3 0.66 26.071.1 24.470.5 1.34 26.071.1 26.171.5 1.34
7 15.170.8 15.873.6 0.2 39.873.8 34.770.4 1.32 58.272.6 61.371.2 1.09 58.272.6 69.373.0 2.8
8 30.071.4 21.374.9 1.71 13.772.8 15.970.3 0.77 20.270.9 18.170.5 1.98 20.270.9 21.671.5 0.78
9 14.770.7 15.272.2 0.23 30.474.5 23.970.4 1.44 31.671.3 32.470.7 0.51 31.671.3 33.372.0 0.71
10 38.171.5 40.577.6 0.31 16.772.6 16.270.2 0.18 1571 15.470.4 0.33 1571 16.671.7 0.81
11 34.571.5 36.077.5 0.2 44.773.7 39.870.4 1.31 47.171.7 48.070.4 0.50 47.171.7 53.672.0 2.44
12 15.470.8 17.573.6 0.56 42.274.1 36.170.7 1.45 45.172.1 45.070.9 0.06 45.172.1 45.673.1 0.13
13 25.571.2 25.474.8 0.01 10.072.7 14.270.2 1.53 16.371.0 15.970.4 0.33 16.371.0 15.071.5 0.72
14 19.471.0 15.673.4 1.06 29.173.6 27.570.3 0.45 29.971.1 28.370.6 1.3 29.971.1 30.871.5 0.46
15 24.171.1 23.974.9 0.04 14.872.9 15.070.2 0.08 19.270.8 16.370.4 3.14 19.270.8 18.071.3 0.79
16 57.072.1 51.079.2 0.64 23.073.3 21.170.3 0.58 31.571.3 23.670.5 5.6 31.571.3 27.572.4 1.46
17 32.871.8 34.777.2 0.25 65.374.4 52.870.4 2.83 41.371.6 43.270.9 1.04 41.371.6 44.372.5 0.99
18 16.871.1 19.573.9 0.65 39.373.7 33.970.4 1.45 51.272.0 52.771.0 0.67 51.272.0 54.272.3 0.98
19 24.571.5 23.674.7 0.17 11.474.0 15.370.2 0.98 18.070.9 17.170.4 0.89 18.070.9 19.171.3 0.67
20 23.675.4 24.970.3 0.25 31.171.2 28.770.6 1.71 31.171.2 33.772.0 1.08

Uncertainties are standard uncertainties.

a
Determined by a-spectrometry.
b
Determined by g-spectrometry.
c 235
Determined by g-spectrometry from the 186 keV line after removal of the U contribution determined by a-spectrometry.

Table 3 Table 4
Statistical comparison based on the w2-test between a- and g-spectrometry Activities (mBq) and Z-score between experimental and theoretical
determination of a radionuclide from its progeny (a ¼ 5%) activities of the 238U and 232Th series radionuclides

a-Emitter g-Progeny n w2 w2n;a P (%) H0 rejected Radionuclide Experimental activity Theoretical activity Zi
238
238
U 234
Th 19 10.3 30.1 94.4 No U series
238
232
Th 228
Ac 20 76.6 31.4 o5 Yes U 32.572.1 32.472.1 0.03
234
232
Th 212
Bi 20 30.7 31.4 6 No Th 33.673.9 32.472.1 0.27
234m
226
Raa 214
Pb–214Bi 20 23.3 31.4 27.4 No Pa 34.1715.7 32.472.1 0.1
234
U 36.972.4 31.572.1 1.71
230
n is the number of soil samples and w2n;a is the critical value at the a level. Th 33.272.0 31.172.0 0.74
a226 226
Ra determined by g-spectrometry through the 186 keV line after Ra 37.174.4 31.172.0 1.24
214
removal of the 235U contribution determined by a-spectrometry. Pb 28.670.8 31.172.0 1.11
214
Bi 28.270.8 31.172.0 1.33
232
for 238U, 232Th, 234Th, and 228Ac. As expected, a-spectro- Th series
232
Th 23.571.6 23.571.6 0
metry is very sensitive, with a detection limit (1–5 mBq/kg) 228
Ac 24.270.6 23.571.6 0.40
typically 1000 times lower than for g-spectrometry 228
Th 32.272.0 23.571.6 3.4
(L’Annunziata, 2003). 224
Ra 18.873.7 23.571.6 1.17
212
Using a-spectrometry, the activity of the first member of Pb 22.970.6 23.571.6 0.37
212
the 238U and 232Th series can be precisely determined. 208
Bi 26.272.5 23.571.6 0.88
Tl 8.370.3 8.570.6 0.23
Thus, the activities of all the progeny can also be
determined by calculation using our ad hoc C-code Z critical value at the level a ¼ 5% is equal to 2. Uncertainties are
program. It assumes that the distribution of the activities standard uncertainties.
of the progeny determined by a- and g-spectrometry can be
compared to the theoretical activities to determine the
validity of the secular equilibrium hypothesis. We designed than expected and the Z-score is significantly higher than
an additional w2-test based on the Z-values between the two. Similar results were obtained for the other 19 soil
experimental and the theoretical activities. samples, where higher 228Th activities than expected were
Tables 4 and 5 show the test results for the most active measured. Measurements of 228Th on the same 20
soil sample analysed in the set. The 238U and 232Th series electrodeposited a-sources were carried out around 2 years
are in equilibrium, with the noticeable exception of 228Th. after electrodeposition. A thorough analysis of the
For this radionuclide, the activity was about 30% higher acquired spectra brought out that excess 228Th observed
 ARTICLE IN PRESS
Saı¨dou et al. / Applied Radiation and Isotopes 66 (2008) 215–222 221

Table 5 necessary after elution of isotopes of thorium. It consists in

Test of secular equilibrium by comparing the experimental results for the
238
depositing 210Po on silver discs before evaporating solution
U and 232Th series with theoretical values calculated using Eq. (9)
for electrodeposition of the isotopes of thorium (Saı̈dou
(a ¼ 5%)
et al., 2007; Vajda et al., 1997).
Radionuclide n w2 w2n;a P (%) H0 rejected Finally, the 235U and 226Ra activities were determined
from the g-spectra of the 20 soil samples after de-
238
U 8 8.1 15.5 42.4 No convolution of the 186 keV multiplet by the Levenberg–
232
Th 7 14 14.1 5.1 No
Marquardt algorithm (Tables 6 and 7). In addition to the
n is the number of radionuclides taken into account in the series. standard uncertainty of Eq. (7), the accuracy of the fit is
estimated to be 3.9% for 235U and 6.3% for 226Ra. In spite
of the difficulty of correctly evaluating the net count rate,
Table 6 the results of the w2-test comparing a-spectrometry to de-
Z-score between activities (Bq/kg) determined by a-spectrometry and convolution of the 186 keV multiplet show that 235U and
activities determined from de-convolution of the 186 keV multiplet by the 226
Ra can be satisfactorily determined using g-spectro-
Levenberg–Marquardt algorithm for the 235U–226Ra pair
metry and de-convolution.
235
Sample Ua 235
Ub Zi Rac
226 226
Rab Zi

1 0.8570.15 0.8470.18 0.047 11.473.0 13.173.3 0.43

8. Conclusions
2 0.6670.17 0.8870.19 0.94 10.473.8 11.973.3 0.32
3 0.8070.18 0.6570.18 0.62 10.874.0 14.373.5 0.73
4 0.6970.16 0.5470.16 0.70 13.273.7 19.273.6 1.36 The environmental radioactivity screening of 20 soil
5 0.8370.13 0.7070.16 0.68 12.273.3 18.173.5 1.44 samples from a region in Cameroon with potential
6 1.1370.23 0.8070.22 1.10 22.573.8 27.974.8 1.10 uranium ore deposits showed normal soil activity
7 1.6770.22 1.5970.33 0.22 39.873.8 47.577.4 1.31
for 238U (12.5–57 Bq/kg). The activity of 232Th was
8 0.7870.17 0.9570.23 0.64 13.772.8 18.274.3 1.05
9 2.070.3 1.7670.47 0.55 30.474.5 50.078.9 2.67 14.6–58.2 Bq/kg.
10 0.8670.16 0.7370.2 0.55 16.772.6 23.374.7 1.56 A statistical comparison of activities measured by
11 1.4770.21 1.6770.29 0.63 44.773.7 54.777.4 1.83 a-spectrometry and g-spectrometry demonstrated that
12 1.7170.24 1.1770.34 1.39 42.274.1 53.278.4 1.67 g-spectrometry is a valid alternative to time-consuming
13 0.8870.17 0.6870.21 0.78 10.072.7 18.874.4 2.08
14 1.1770.22 0.8770.21 1.05 29.173.6 39.275.5 2.12
a-spectrometry for natural uranium and thorium determi-
15 0.7970.17 0.5470.19 1.04 14.872.9 22.974.2 2.0 nation in soil. g-Spectrometry makes it possible to carry
16 0.9870.20 1.2870.24 1.08 23.073.3 26.074.8 0.65 out large-scale screening of soil samples. However, when
17 2.170.2 2.270.38 0.26 65.374.4 78.3710.2 1.88 the activity of the sample to be measured is less than its
18 1.4970.21 1.8370.33 1.0 39.373.7 42.576.8 0.57 g-spectrometry MDA, a-spectrometry must still be used.
19 1.1270.26 0.6870.19 1.41 11.474.0 20.574.1 1.86
The 238U and 232Th series of natural radioactivity are in
20 1.3070.35 1.1070.26 0.48 23.675.4 35.775.9 1.84
secular equilibrium and attention should be focused on
228
a
Determined by a-spectrometry. Th that interferes with 210Po. Thus, an additional stage
b
Determined by de-convolution of the 186 g-line by the Levenberg–- that consists in depositing 210Po on silver discs would be
Marquardt algorithm.
c advisable after elution of isotopes of thorium and before
Determined by g-spectrometry of the 186 keV line after removal of the
235
U contribution determined by a-spectrometry. electrodeposition.
For de-convolution of the 186 keV multiplet, the
Levenberg–Marquardt algorithm is a suitable method for
Table 7 determining the activities of 235U and 226Ra. However,
Comparison of a/g-spectrometry results and de-convolution of the although the computation time is short, the method
186 keV peak by the Levenberg–Marquardt algorithm for the
235 requires careful selection of the initial values for the
U–226Ra pair (a ¼ 5%)
parameters by the user. The de-convolution of 186 keV
Radionuclide N w2 w2n;a P (%) H0 rejected doublet may have substantial problems if 235U and 226Ra
activities differ a lot. Therefore, the use of external
235
226
U 20 12.1 31.4 89.7 No information on 235U activity (through a-spectrometry or
Ra 20 28.5 31.4 9.8 No
through minor lines of 235U) is beneficial in those cases.
n is the number of soil samples.

was mainly due to interference (Sanchez et al., 1996)
between a-lines of 228Th (5.34 MeV) and 210Po (5.30 MeV)
which is a short-live radionuclide (T1/2 ¼ 138.4 d). Thus, it
is important to underline that fusion of soil samples
undertaken before chemical separation did not entirely
volatilise 210Po. Finally, an additional stage would be
Acknowledgements
We would like to thank the Swiss Federal Commission
for Scholarships for Foreign Students for grant,
T. Buchillier for gamma-ray spectrometer calibration,
Dr. S. Bulling for English corrections, M. Ngachin and
M. Ngoko Djiokap for sampling.
 ARTICLE IN PRESS
222 Saı¨dou et al. / Applied Radiation and Isotopes 66 (2008) 215–222
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