USE OF GAMMA-RAY SPECTROMETRY FOR URANIUM ISOTOPIC

ANALYSIS IN ENVIRONMENTAL SAMPLES

Y.Y. EBAID
Physics Department, Faculty of Science, Fayoum University, Fayoum, 63514 Egypt
Email: yebaid@yahoo.com
Received February 18, 2009

Gamma-ray spectrometry was employed to determine the uranium isotopic

ratios (235U/238U) in the environmental samples. A simple mathematical formula was
derived and used to easily determine the 235U in any environmental sample, regardless
of 238U equilibrium status. Also the adopted formula could be used for all types of
environmental samples with different uranium isotopic ratios.
Key words: Uranium isotopic ratio, gamma-ray spectrometry

1. INTRODUCTION

Uranium is a rare earth element found in the earth’s crust with an average of
3 ppm. Natural uranium is a mixture of three radioactive isotopes 238U (99.27%
abundance), 235U (0.72% abundance) and 234U (0.0054% abundance). It has been
employed over the last seven decades as a source of energy and weapon.
Enrichment processes were widely practiced to produce the necessary fuel. On the
other hand, depleted uranium (DU) was also produced as a by-product of this
enrichment processes. It was successfully used in many fields e.g. for shielding
gamma radiation, penetrating calibers and as ballasts in aircrafts. Accordingly,
monitoring of the isotopic 235U/238U ratio could be a good indicative of the origin
and/or activities associated with any uranium containing samples.
Gamma-ray spectrometry is a powerful non-destructive analytical tool to
determine the gamma emitters both qualitatively and quantitatively. Hyper-pure
germanium detectors (HpGe) are widely used for gamma spectrometry
measurements. They are favored over other detectors due to their distinctive
resolving power. However, some photo-peaks from different radionuclides could
still overlap together because of the proximity in their energy values so that the
difference between them is less than the resolving power. An explicit example of
that is the interference between the 185.7 keV photopeak of the 235U and the 186.1 keV
photopeak of the 226Ra with branching ratios (f-value) of 57.2 % and of 3.5% for 235U and
226
Ra respectively [1]. This problem could be easily handled if the radionuclide of interest

Rom. Journ. Phys., Vol. 55, Nos. 1–2, P. 69–74, Bucharest, 2010
70 Y.Y. Ebaid 2

has another gamma transitions with reasonable f-values. Additionally, the occurrence
of secular equilibrium between certain radionuclide and its respective progenies
could be very helpful to determine the parent's activity whenever they have the
appropriate gamma transitions e.g. 226Ra and its progenies 214Pb and 214Bi.
Environmental samples could pose a potential challenge when they are
measured for both natural uranium and radium. This is because of the explicit
interference between the 185.7 keV photopeak of the 235U and the 186.1 keV
photopeak of the 226Ra. So, a mathematical treatment should be performed to
extract the net counts contributed by each radionuclide [2]. This study is going to
mathematically treat the relations between the 226Ra, 235U and 238U count rates due
to their gamma transitions in order to easily calculate both uranium isotopes and to
distinguish between samples containing normal, enriched and depleted uranium.
In order to accurately determine the 235U/238U isotopic ratio in environmental
samples using gamma-ray spectrometry, careful measurement using precise
efficiency calibration should be performed. Uranium-238 could be estimated
precisely using the 1001.03 keV (0.837 %) of 234mPa. The most predominant
gamma transition 185.7 keV (57.2 %) is preferred to measure the 235U. The reason
that the 143.76 keV (10.96 %), 163.33 keV (5.08 %) and 205.31 keV (5.01 %)
energy transitions are not commonly used to determine 235U in environmental
samples is mainly due to their relatively lower branching ratios compared to that of
the 185.7 keV energy transition. According to the average normal concentrations of
235
U in the environmental samples, counting rates due to the 143.76 keV, 163.33
keV and 205.31 keV energy transitions would be below the detection limits ranges
for the HpGe detector. So it is more practical to use the 185.7 keV energy
transition to assess the 235U. Accordingly it is necessary to set up some equations to
express for the concentration of 226Ra, 235U and 238U isotopes separately.

2. THEORETICAL CALCULATIONS

The activity of a specific radionuclide with a gamma energy transition could

be expressed using the following equation:
C ( E , n)
A= (1)
t. f ( E , n).ε ( E , n)
where:
A: activity concentration of radionuclides n
C: the net photopeak count
t: counting time, s,
f: branching ratio, number of photon with energy E per hundred disintegration,
ε : is the detection efficiency.
3 Uranium isotopic analysis in environmental samples 71

In this study we use the assumption that secular equilibrium is not necessarily
existed between 238U and its progeny 226Ra. Determination of the radionuclide 226Ra
is often performed using the most intensive gamma transitions of its progenies,
214
Pb and 214Bi, following a secular equilibrium of at least 30 days after samples
being sealed. The energy transitions used are 295.2 keV (18.5%) and 351.9 keV
(35.8%) of the 214Pb isotope and 609.3 keV (44.8%) and 1120.3 keV (14.8%) of the
214
Bi isotope. So a good sealing of the samples container for at least 30 days should
be essential so that no radon escape during this 30 day is allowed to avoid
disequilibrium problems between 226Ra and its respective progenies. Also, 238U is
frequently estimated using the energy transitions of 63.3 keV (3.6%) and 92.6
(4.9%) of the 234Th (Direct daughter of 238U). Several restrictions draw attention to
the use of these two lines to determine 238U due to the interferences and self
absorption [3]. A simple mathematical calculation was provided by [2] to
determine 238U, 235U and 226Ra in the environmental samples concluded that.
0.036 ARa
CRRa/CRU5 = (2)
0.572 AU
Where CRRa: is the count rate (counts.sec-1) due to 226Ra in the 186 keV
energy peak.
CRU5: is the count rate (counts. sec–1) due to 235U in the 186 keV energy peak.
ARa: is the activity of 226Ra in the sample
AU5: is the activity of 235U in the sample
This resulted in the formulae (3) and (4) for samples with secular
equilibrium.
CRRa = 0.583⋅CRT (3)
and CRU5 = 0.417⋅CRT (4)
Where CRT: is the total count rate (counts. sec–1) in the 186 keV energy peak.
Ebaid, et al., 2005, assumed that the samples do not contain uranium isotopic
ratios anomalies [2].
In this study we need to deduce a simple formula to calculate the 235U activity
in any environmental sample using its most predominant gamma transition
185.7 keV (57.2%).
CRU 5
AU 5 = (5)
ξ186 keV ⋅ fU 5(185.7 keV )
while CRU 5 = CRTotal (186.0 keV ) − CRRa (186.0 keV ) (6)

CRTotal (186.0 keV ) − CRRa (186.0 keV )

So AU 5 = (7)
ξ186 keV ⋅ fU 5(185.7 keV )
72 Y.Y. Ebaid 4

Also CRRa(186.0 keV) could be calculated using the activity of the 214Bi isotope in
equilibrium with its parent the 226Ra using the 609.3 keV (44.8%) energy transition.
Accordingly, the equation will be as follows;

CRTotal (186.0 keV ) −  ABi − 214 ⋅ ξ186 keV ⋅ f Ra (186.0 keV ) 

AU 5 = (8)
ξ186 keV ⋅ fU 5(185.7 keV )

 CRBi (609.3keV ) 
CRTotal (186.0 keV ) −  ⋅ ξ186 keV ⋅ f Ra (186.0 keV ) 
And AU 5  ξ Bi (609.3keV ) ⋅ f Bi (609.3keV )  (9)
=
ξ186 keV ⋅ fU 5(185.7 keV )
By using the reference values for the f-values in the equation, the equation will be;

 CRBi (609.3keV ) 
CRTotal (186.0 keV ) −  ⋅ ξ186 keV ⋅ 0.036 
And AU 5 =  ξ Bi (609.3keV ) ⋅ f Bi (609.3keV )  (10)
ξ186 keV ⋅ 0.572
So the formula will be;
 CRTotal (186.0 keV )   CRBi (609.3keV ) 
AU 5 = 1.75   − 0.063   (11)
 ξ186 keV   ξ Bi (609.3keV ) ⋅ f Bi (609.3keV ) 
 CRTotal (186.0 keV ) 
And finally AU 5 = 1.75   − 0.063 ( ARa − 226 ) (12)
 ξ186 keV 
Using equation (12) we can easily calculate the 235U content of any sample
containing 226Ra as an interfering radionuclide. Additionally, Uranium isotopic
ratios could be calculated using the 238U results calculated from the 1001 keV
transition energy. It is worthy to mention that both the detection efficiencies ( ε ):
at 185.7 keV and 186.2 were considered the same for simplicity since the
difference would be minimal.

3. EXPERIMENTAL

Three different samples were measured for their uranium isotopic contents
and ratios in this study. Uranium ore reference (IAEA-RGU-1) soil sample, natural
uranium standard solution, and commercial Uranyl nitrate solution were measured
to estimate their uranium isotopic ratios. Three identical aliquot (75 ml) were used
from each sample to minimize the statistical error.
5 Uranium isotopic analysis in environmental samples 73

Gamma-ray spectrometer with a GX4019-7500Sl CANBERRA extended

range electrode germanium detector with a CANBERRA model 2002CSL
preamplifier was used for this work. The HpGe detector had a relative efficiency of
40% and full width at half maximum (FWHM) of 1.9 keV for 60Co gamma energy
transition at 1332.5 keV. Samples were counted for 86,400 seconds to achieve
minimum photo-peak fitting errors. The system was calibrated for photopeak
efficiency using standard soil sample in the same geometry for the studied samples.
The energy transition of 185.7 keV were used to estimate 235U contents, while the
energy transition of 1001 keV was used to calculate the 238U contents. Uranium-
235 was calculated for the RGU-1 samples after using our current equation.
Correction for both matrix and density were performed according to methods
adopted by Khater and Ebaid, 2008, and Ebaid, 2009 [4, 5].
The uranyl nitrate sample was also measured using alpha spectrometry
technique. Diluted aliquot of the original solution was used to determine the
isotopic uranium contents. Sample was first co precipitated using ammonium
phosphomolebdate to precipitate the uranium from the solution. The samples were
dissolved using 6 M Nitric acid and then run through strong anion exchange resin
followed by electro-chemical plating. Silicon Surface barrier detector was used to
count the samples for 24 h to reach minimum counting error.

4. RESULTS AND DISCUSSIONS

Table 1 shows the calculated 235U and 238U in the studied samples in Bq.kg–1
using gamma-ray spectrometry. Only RGU-1 sample contains 226Ra in equilibrium
with 238U. It could be noticed that the obtained isotopic uranium ratios are in
accordance with the certified values. On the other hand, both the natural uranium
and Uranyl nitrate solutions contain uranium only with the absence of 226Ra. The
formula was successful to be used for all types of samples. It can also be noticed
that the resultant isotopic uranium ratio for the natural uranium solution is also in
accordance with the certified value.

Table 1
-1 235 238
Specific activities (Bq.kg ) of U and U and 235U/238U ratios in the studied samples using gamma-
ray spectrometry
235 238 235
Sample U U U/238U Ratio
Certified Calculated Bias %
RGU-1 20.5 ± 1.1 413.2 ± 12.4 0.046 0.050 8.7
Natural Uranium 11.1 ± 0.6 241.0 ± 7.2 0.046 0.042 –8.7
Standard Solution
Uranyl Nitrate Solution 10.54 ± 0.5 437.8.0 ± 13.1 NA 0.024 NA
74 Y.Y. Ebaid 6

Table 2
234 238
The calculated U and U in two different concentrations of uranyl nitrate solutions in mBq.kg-1
using alpha spectrometry
234 238 234
Sample U U U/238U
Uranyl Nitrate-1 45.8 ± 2.2 115.7 ± 3.5 0.395
Uranyl Nitrate-2 230.0 ± 7.0 571.7 ± 17.1 0.402

According to this formula we were able to assess how far the commercial
uranyl nitrate is depleted. The isotopic ratio was found to be 0.024 compared to a
normal ratio of 0.046. This formula might help is the assessment of the uranium
isotopic ratio in any environmental samples regardless of both their 238U-226Ra
equilibrium status and their uranium isotopic ratios
On the other hand, alpha spectrometry results shown in Table 2 were very
efficient in the determination of both 234U and 238U in the samples. However, the
determination of 235U was so crucial because it has several alpha emissions. Among
those emissions, there are four major alpha particle energies of 4214.7, keV
4366.1, keV 4397.8, and keV 4596.4 keV with intensities of 6.4%, 17%, 57%, and
5.6% respectively. Accordingly, it was a challenging process to calculate the total
counts due to the 235U.

CONCLUSION

It is recommended to use gamma-ray spectrometry as a non-destructive and

relatively simple technique to assess the uranium isotopic ratios in environmental
samples in order to investigate their status regarding being normal, enriched or
depleted. This technique is highly recommended to perform environmental
safeguard analyses for all types of environmental samples.

REFERENCES

1. J.U. Delgado, J. Morel, M. Etcheverry, Measurements of photon emission probabilities from the
decay of 226Ra and daughters, Appl. Radiat. Isot., 56, 137–143, 2002.
2. Y.Y. Ebaid, S.A. El-Mongy, K.A. Allam, 235U–γ emission contribution to the 186 keV energy
transition of 226Ra in environmental samples activity calculations, International Congress
Series 1276, 409–411, 2005.
3. Z. Papp, Z. Dezso, S. Daroczy, Measurement of the Radioactivity of 238U, 232Th, 226Ra, 137Cs and
40
K in Soil using Direct Ge(Li) γ-ray Spectroscopy, J. Radioanal. Nucl. Chem.. 222 (1–2),
171–176, 1997.
4. A.E.M. Khater, Y.Y. Ebaid, A simplified gamma-ray self-attenuation correction in bulk samples,
Appl. Rad. Isot., 66, 407–413, 2008.
5. Y.Y. Ebaid, On the use of reference materials in gamma-ray spectrometric efficiency calibration
for environmental samples, J. Radioanal. Nucl. Chem., 280, No. 1, 21–25, 2009.