Applied Geochemistry 37 (2013) 203–211

Contents lists available at ScienceDirect

Applied Geochemistry
journal homepage: www.elsevier.com/locate/apgeochem

Natural and depleted uranium in the topsoil of Qatar: Is it something to

worry about?
Basem Shomar a,⇑, Mohamed Amr b, Khalid Al-Saad b, Yasir Mohieldeen a
a
Qatar Environment and Energy Research Institute (QEERI), Qatar Foundation, P.O. Box 5825, Doha, Qatar
b
Central Laboratory Unit, Qatar University, P.O. Box 2713, Doha, Qatar

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

Article history: This study examines uranium in soils of Qatar to investigate whether there is any detectable traces of
Received 7 April 2013 depleted uranium (DU). 409 soil samples were collected using a 10 km grid system throughout the State
Accepted 1 August 2013 of Qatar. The U concentrations and isotopic compositions (235U/238U) were determined using an ICP-MS.
Available online 12 August 2013
The U concentrations range from 0.05 to 4.7 mg/kg and the 235U/238U isotopic signatures are in the range
Editorial handling by M. Kersten
0.007–0.008, i.e. comparable to the isotopic ratio in natural uranium (NU). The distribution of these con-
centrations in the topsoil were used to see correlations with locations of pollution point sources and envi-
ronmentally hot areas associated with human activity: industrial estates, solid waste dumping sites,
wastewater treatment plants, sea harbors, airports, and public transport network. New thematic maps
were built using Geographic Information System (GIS) software. The results showed that there is no link-
age between the occurrence, distribution, concentrations and isotopic ratios of U and these hotspots.
More importantly, due to the low concentration of organic matter (OM) in soils of Qatar, very limited
P-fertilization, the alkaline nature of soil (pH 8) and low Fe/Mn contents make soil uranium concentra-
tions very low. The residential areas, including the capital Doha, had the lowest total concentrations of
uranium and isotopic ratios of the country while the northern and western parts showed the highest
values.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction Secondary uranium mineralization of Quaternary age is formed

Uranium (U) is a naturally occurring element found in low lev-
els within rock, soil, and water (UNSCEAR, 1993). U concentrations
in soil naturally range between 300 lg/kg and 11.7 mg/kg (Kabata-
Pendias and Pendias, 2000). The occurrence, source, distribution,
concentration, mobility, and the speciation of uranium in the soil
environment depend on both natural and anthropogenic factors.
Naturally, U is released into solution by weathering of primary
minerals; therefore uranium occurrence varies with climate and
underlying bedrock conditions (Gueniot et al., 1988).
In soils, uranium mobility is influenced by soil type and phys-
ico-chemical properties (Echevarria et al., 2001). Several uranium
minerals in soil of arid areas could be formed by weathering, dia-
genetically during soil formation or sedimentation processes (Ilani
and Strull, 1989) where NU concentration ranged between 200 and
3900 mg/kg. Two distinct types of uranium mineralization may oc-
cur in arid soils: primary and secondary types. Primary uranium
mineralization is represented by uranium enrichments in phos-
phorites of sedimentary phosphate deposits age as well as by ura-
nium anomalies associated with epigenetic iron-oxide veins.
⇑ Corresponding author. Tel.: +974 4454 2872; fax: +974 4454 1528.
E-mail address: bshomar@qf.org.qa (B. Shomar).
by weathering and soil formation processes under arid conditions.
The secondary uranium minerals are associated with gypsum rich
crusts and veins in the soils (Ilani and Strull, 1989). Minerals of U
(e.g. meta-autunite, meta-tyuyamunite and carnotite) are associ-
ated with ions of vanadate, phosphate and carbonate. Secondary
uranium minerals are associated with gypsum which forms thin
veins and is found also as a matrix in pedogenic layers that range
from 0.2 to 1.5 m in thickness (Ilani and Strull, 1989).
Echevarria et al. (2001) measured the uranium sorption ratios
and found that they are affected by soil type and chemical compo-
sition. Additionally, soil pH is highly linearly correlated with the
logarithm of uranium sorption ratios. At the same time, U sorption
behavior depends on the occurrence of uranium oxide and carbon-
ate complexes. The study by Gueniot et al. (1988) indicated that
soils rich in iron and aluminum but still conserving a substantial
amount of silica showed the largest U accumulation, while soils
with only iron and aluminum oxides remaining, and minor kaolin-
ite, showed significant depletion of U. A strong association be-
tween Fe-oxides and soil uranium has been found (Pett-Ridge
et al., 2007). Moreover, the study found that soil U contents in-
crease between 20-fold and 60-fold with age along the
chronosequence.
Depleted uranium (DU) has been used extensively during weap-
ons testing and recent military conflicts (Handley-Sidhu et al.,

0883-2927/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apgeochem.2013.08.001
204 B. Shomar et al. / Applied Geochemistry 37 (2013) 203–211
2010). The firing of weapons containing depleted uranium (DU)
during conflicts and military testing has resulted in the deposition
of DU in a variety of sand-rich environments (Handley-Sidhu et al.,
2009). The 1991 Gulf War alone resulted in the deposition of 321
tons of DU into the desert regions of Kuwait and Iraq (Handley-Sid-
hu et al., 2009). Test firing of DU-containing weapons at military
ranges have also deposited DU in sand-rich environments, such
as the Yuma Proving Ground, USA desert environment (Johnson
et al., 2004), dune sands of the Eskmeals range, UK (ca. 15 tons)
(Toque and Baker, 2006) and terrestrial and marine sediments of
the Aberdeen Proving Ground, USA (>70 tons of DU) (Dong et al.,
2006).
Uranium is classified as ‘‘very toxic’’ (Health and Safety Execu-
tive, 1995), causing skin, lung, intestinal and bone marrow disor-
ders, particularly where individuals have been chronically
exposed by skin contact, direct ingestion or inhalation of dust
(such as in mines and processing). U is taken-up by plants but most
U ingested from food and water is excreted and does not remain in
the body (Taylor, 1997). All three main isotopes of U (235U, 236U,
Fig. 1. Base map of Qatar showing the land use.
238
U) are radioactive alpha emitters with long half-lives (Jones
et al., 1990). Naturally occurring uranium is composed of three ma-
jor isotopes, uranium-238 (99.2739–99.2752% natural abundance),
uranium-235 (0.7198–0.7202%), and uranium-234 (0.0050–
0.0059%) (Wikipedia, 2013).
For the general population, chemical toxicity by inhalation of
dust or direct ingestion is considered a greater hazard than radio-
active toxicity (Menzel, 1968). Although less radioactive, DU has
the same chemotoxicity as natural uranium and poses a threat to
an exposed human populations (Bleise et al., 2003; Choy et al.,
2006).
Iraq, a near neighbor to Qatar, has received extensive (400 ton-
nes) DU contamination from the two wars in 1991 and 2003, and
the predicted cost for remediating the 300 sites is about US$ 30
Million (Dutch Peace Group, 2013). In the State of Qatar, no analy-
sis of NU and DU contents of topsoils currently exist, therefore the
objectives of this study were to (1) determine the occurrence and
distribution of natural and depleted uranium in the topsoil of Qa-
tar; (2) use GIS to assess the impacts of current land use and envi-
 B. Shomar et al. / Applied Geochemistry 37 (2013) 203–211
ronmental hotspots (industrial estates, wastewater treatment
plants, solid waste dumping sites, road networks) on the occur-
rence of uranium in soil; and (3) assess the potential exposure risks
associated with natural and depleted uranium in Qatar’s topsoil.
2. Study area, thematic maps and sampling strategy
2.1. Study area
Qatar (Fig. 1) a small desert country with an area of 11,493 km2
is characterized by its arid to hyper-arid climate. Due to rapid eco-
nomic growth, the population increased from about 0.744 to 1.7
million during the years 2000–2010, and over 85% of the popula-
tion is concentrated in the urban, coastal area of the capital, Doha
City (The Planning Council, 2012).
The elevation of Qatar decreases from 100 m above sea level in
the south to less than 50 m in the north. Qatar is a rocky desert
area with scattered oases formed by 850 separate depressions. In
these depressions colluvial soils made up of calcareous loam, sandy
loam and sandy clay loam have accumulated to depths ranging
Fig. 2. Environmental hotspots in the State of Qatar.
205
from 30 to 150 cm, overlying limestone debris and bedrock. These
depression soils are locally known as Rodat and constitute the
main agricultural soils of the country. Highly saline depression
soils, locally known as Sabkha, occur mainly along the coasts of
Umm Said, Dukhan and the southern boundary of Qatar. In south-
ern Qatar, the depressions are often more crater-like in appear-
ance, with the bottoms usually covered by Aeolian sands (Abu
Sukar et al., 2007; Awiplan Qatar and Jena-Geos, 2005).
Rainfall is extremely unpredictable and highly erratic, both in
time and space. Because of its low intensity and variability, it is
not considered reliable for supplementing irrigation and maintain-
ing agriculture, yet it represents the main source of water in the
form of recharge to groundwater.
Qatar is an arid country of harsh and fragile environment, high
summer temperature (>40 °C), low rainfall (annual average is
82 mm) with a high evaporation rate (annual average of
2200 mm), and low nutrient availability in the soil (Darwish and
Mohtar, 2012). The municipal potable water consists of 99% de-
salted seawater and 1% groundwater.
206 B. Shomar et al. / Applied Geochemistry 37 (2013) 203–211
2.2. Thematic maps
Data used in deriving the U distribution maps were collected
from sampling locations that were demarcated using a Global Posi-
tioning System (GPS). The sampled locations were then positioned
in the maps using Geographic Information System (GIS). The Geo-
statistics tool in ArcGIS was used to interpolate the concentration
and distribution of the U in the topsoil of Qatar. Geostatstics was
used as it provides accurate and diverse interpolation functional-
ities (ESRI, 2012; Zhang et al., 2008). GIS was also used to carry
out the thematic mapping which includes: a land use, soil types,
and environmental hotspots map.
The mapping was carried out using data from different sources.
The base maps, such as international boundaries, roads, and coast
line, were obtained from the Ministry of Environment, Qatar in dig-
ital format. Industrial areas and locations of wastewater treatment
plants were scanned and digitized from 1:20,000 maps found in
the Qatar National Atlas published by the Planning Council of
Qatar.
Fig. 3. Soil sampling locations.
Finally, the thematic maps for land use (Fig. 1), environmental
hotspots (Fig. 2), sampling locations (Fig. 3), soil types (Fig. 4),
and U contaminant concentrations and distribution in the topsoil
of Qatar have been constructed.
2.3. Sampling strategy
The soil-sampling campaigns were conducted according to the
European soil-sampling guidelines (Theocharopoulos et al., 2001).
For systematic sampling, the country was divided into a 10 km2
grid (Fig. 3) and one composite sample (consisting of 10 subsam-
ples) was collected from each square. The criteria for the sampling
area, specific site, and point selection were based primarily on
pedology, land use, and geology. At each sampling site, a circle of
5 m in diameter was identified and 10 subsamples were collected
within the perimeter. Debris (plant tissue, stones, etc.) were re-
moved and approximately 0.5 kg of topsoil were placed into poly-
ethylene cups and stored at 4 °C. The location of each sample
(within a typical resolution of 5 m) was recorded using the GPS
 B. Shomar et al. / Applied Geochemistry 37 (2013) 203–211
coordinates (x, y and z) which have been used to build the map of
sampling locations. Fig. 4 shows the comprehensive sampling of
Qatari soils.
3. Sample preparation, instrumentation and sample analysis
3.1. Soil preparation, digestion, and total uranium determination
After drying in a vacuum oven at 45 °C, approximately 0.5 kg
soil samples were manually ground and sieved through a 20-lm
sieve and ground to a very fine powder by using a sand mill (FRIT-
SCH-Labor Planeten Mühle, Pulverisette 5). Soil samples were dried
overnight at 105 °C. About 0.5 g of each sample was weighed and
transferred into a PTFE beaker. Ten mL of HF (40%) and 4 mL of
HClO4 (70%) were slowly added and evaporated on a hot plate at
200 °C until a crystalline paste was formed (2–3 h). Four mL of
HClO4 was added to each sample and evaporated to near dryness
to remove any HF residue. Ten mL of 5 M HNO3 was added and
warmed gently until a clear solution was obtained. The clear solu-
Fig. 4. Types of soil in Qatar.
207
tions of samples were allowed to cool down and then diluted to
50 mL in polypropylene bottles for storage (producing a 1 M
HNO3 solution). One mL of aliquot was diluted to 10 mL of deion-
ized water, immediately prior to analysis by the inductively cou-
pled plasma mass spectrometry (ICP-MS) (Agilent, 7500Ce). More
information is given in Al-Saad et al. (2010).
3.2. Determination of uranium isotopes using ICP-MS
The only evidence of DU contamination in data for soil samples
from this study would be the disruption of the natural isotopic
abundance of 238U and 235U. From the natural isotopic abundance
of the uranium isotopes (99.2% for 238U, and 0.72% for 235U), the
activity ratio of natural uranium is calculated to
235
U/238U = 0.00725. If this ratio is significantly higher than
0.00725, it would be evidence that the analyzed sample contains
DU (Anagnostakis et al., 2001).
The ICP-MS using a micromist nebulizer, which was fitted into a
standard quartz double-pass spray chamber, was operated at 2 °C
208 B. Shomar et al. / Applied Geochemistry 37 (2013) 203–211
to ensure temperature stability and reduce the water vapor present
in the carrier gas/aerosol stream. Shield torch was used to increase
the sensitivity. The sensitivity of ICP-MS was optimized for a max-
imum ion intensity of 238U isotope (Lloyd et al., 2009; Oliver et al.,
2008; Bednar et al., 2007; Pawlak and Rabiega, 2002).
The plasma power was 1200 W with a nebulizer flow of
0.85 mL/min. Samples were prepared for analysis by filtration
(0.45 lm unless otherwise specified) and acidification to pH 2 with
nitric acid, unless otherwise specified. Because of its rarity in most
samples and its similar mass to 238U, bismuth (209Bi as bismuth ni-
trate, J.T. Baker, Phillipsburg, NJ) was used as the internal standard
for all analyses.
3.3. QC/QA
Certified reference materials (CRM) for both NU (NIST 4321C)
and DU (NIST 3164) were used and treated exactly the same as
the samples. An additional uranium analytical calibration standard
(10 mg/L) was purchased from SPEX Certiprep (SQS-01-1, Accu-
Fig. 5. Concentration of natural uranium in the topsoil of Qatar.
Trace, AccuStandard, Inc., New Haven, CT, USA). Nitric acid, hydro-
fluoric acid, and perchloric acid were obtained from Merck,
Germany.
For instrumentation, the ICP-MS was used for determination of
uranium in digested samples because of its higher sensitivity and
faster analysis speed than traditional sodium iodide gamma spec-
troscopy. A detection limit of 0.05 lg/L in aqueous solution
(0.1 mg/kg in soil) was determined for direct nebulization ICP-MS
analysis, and is in agreement with the literature (Pawlak and Rab-
iega, 2002).
4. Results
The average results have been calculated as well as the standard
deviation for all soil samples (n = 409). The corresponding maps for
the concentrations of total uranium and the isotopic ratios are gi-
ven in Figs. 5 and 6, respectively. The results showed a maximum
concentration of U in topsoil of 5 mg/kg which is within the natural
range of U in soil (A Supplementary table is available). The concen-
 B. Shomar et al. / Applied Geochemistry 37 (2013) 203–211
Fig. 6. Uranium isotopic ratios in the topsoil of Qatar. Natural uranium (NU) has
trations of total uranium varied from 0.05 to 4.6 mg/kg and aver-
aged 1.63 ± 0.6 mg/kg.
The 235U/238U ratios were consistent throughout the country
with no significant variations among different types of soils or in
varying locations. Fig. 6 shows a variation of 235U/238U ranging
from about 0.0065–0.0079, or about ±10% on any given ratio. The
natural ratio of uranium, 0.0072, falls within this range. To esti-
mate the anthropogenic uranium (DU), the 235U/238U ratios of the
409 soil samples have been subtracted from the natural back-
ground ratio (Anagnostakis et al., 2001). With this calculation, it
has been found that the results of 235U/238U ratio for all soil sam-
ples were less than the natural background ratio indicating no
DU contamination. The background 235U/238U ratio in Qatar
(0.0075) was determined using 10 soil samples obtained from
depths of 50 to 100 cm at different sites. The data show no
depth-dependent variation, confirmed the limited introduction of
anthropogenic U into the surface soils.
There were no observed correlations between the distribution
of total uranium and isotopic ratios, and the identified environ-
mental hotspots (locations of industrial activities, traffic network,
solid waste dumping sites, wastewater treatment plants and sea
or airports).
209
235
U/238U = 0.00725.
5. Discussion
It is clear that soil types of Qatar and the occurrence of uranium
on it is logical and consistent. The soils of Qatar are mostly calcar-
eous and the pH is alkaline (about 8). The pH–Eh diagrams of ura-
nium obtained from Choy et al. (2006) showed that the low pH and
high Eh conditions prevented the formation of solid U compounds
such as uraninite and schoepite. However; schoepite has been
shown in several studies to form in calcareous, well aerated soils
of the southwest of the USA (Buck et al., 2004; Johnson et al., 2004).
The diagrams indicate that U(VI) cationic complexes are abun-
dant at slightly alkaline pH (about pH 8) only if the soil is rich in
organic matter which is not the case of Qatar. Uranium tends to
form stable aqueous complexes and precipitates with organic li-
gands (Murphy and Shock, 1999). The findings of this study agree
with Bednar et al. (2007) where the soil of Qatar is very poor on or-
ganic matter (Fig. 4). This could explain the low contents of ura-
nium in the topsoil of Qatar as a result of very low concentration
of organic matter in the sandy and dry soil. Moreover, Laubenstein
and Magaldi (2008) studied the occurrence of uranium and other
elements in several Mediterranean soils and they confirmed that
soils characterized by absence or scarcity of 2:1 clay minerals are
210 B. Shomar et al. / Applied Geochemistry 37 (2013) 203–211
poor in uranium. This shows that the rich soil carbonate of Qatar
associated with natural ranges of NU which may go up to 5 mg/
kg. This agrees again with the findings of Laubenstein and Magaldi
(2008) where average uranium concentration in carbonate rocks is
2.2 mg/kg due to the fact that uranium can replace calcium in the
lattice of calcite or be adsorbed by the principal phosphate
minerals.
Four major factors may play roles on the occurrence (mobility/
immobility) of uranium in soil; the soil pH, the organic matter
(OM), the microbial community, the Fe and Mn oxides and the car-
bonate complexes. It is believed that the major role is the pH (Lin-
hoff et al., 2011; Moncur et al., 2011).
In the alkaline desert environment, several studies have found
strong enrichment of U in groundwater (Kumar et al., 2011)
which has given rise to soda lakes highly enriched in uranium.
The low level of U in soil may reflect the mobilization of U(VI) as
stable carbonate complexes transferred to groundwater and soda
lakes (Jurgens et al., 2009; Kumar et al., 2011; Moncur et al.,
2011; Nriagu et al., 2012).
Under normal conditions, it is documented that organic matter
in soil is a key factor to attract uranium. Occurrence of organic
matter in the surface soil may enhance the formation of organo-
uranium complexes in a variety of soils and plant materials, indi-
cating that nearly 100% of the uranium extracted from certain
plant tissues is bound to organic ligands. On the other hand, Bed-
nar et al. (2007) found that soil humic acid generally decreased
uranium sorption to soils and promoted subsequent desorption
of uranium because of uranium partitioning to the organic phase
which may illustrate that organic compounds influence the mobil-
ity and chemistry of uranium in the environment. Moreover, the
soil of Qatar is poor in clay minerals and it is generally agreed that
U binds to soil clays and to organic matter, and is only moderately
mobile under oxidizing conditions (Taylor, 1997). The weak rela-
tionship between U and OM in soil could be related to the fact that
uranium is a very big molecule which cannot fit to any structure of
OM and it cannot replace any other cations in organic matter such
as Cu and Zn. No strong correlations have been found between the
presence of OM and U in soil (Kumar et al., 2011).
The map of land use (Fig. 1) showed that the agriculture sector
is very limited and more than 99% of food vegetables are imported.
The soils collected from agricultural lands showed normal concen-
trations of U. Other agricultural areas such as southern Europe,
Australia and New Zealand show higher concentrations of U in soil.
The agricultural practices and application of phosphate fertilizers
are the main sources of the potentially toxic uranium in New Zea-
land (Schipper et al., 2011). The changes in total U were directly re-
lated to the type and amount of P fertilizer applied and it is found
that there were generally linear increases in total P and total U in
these agricultural soils. Correlation between U and P in soil showed
that maximum concentration of U (2.8 mg/kg) was associated with
100 kg P/ha treatment (Schipper et al., 2011), which is still within
the natural U background in topsoil. It is believed that phosphate
rocks used to manufacture P fertilizer contain elevated levels of
some trace elements including uranium and top-dressing with P
fertilizer can result in higher concentrations of U in surface soil
(Schipper et al., 2011).
The very limited studies on soil chemistry of Qatar showed very
low concentrations of Fe and Mn. A new comprehensive study will
start soon. U is associated with carbonate, Fe and Mn oxides and
organic matter fractions of the material in soil. Additionally, it is
associated with soil particle size where Choy et al. (2006) found
that fine fractions (particle diameter <0.075 mm) contained total
U of 7732 mg/kg. An additional factor which may enhance the
occurrence of U in soil is the presence of some microorganisms.
As the soil of Qatar is poor and dry, the microorganism communi-
ties are also poor. Again, the aridity of soil in Qatar, the absence of
organic matter and active microorganisms may explain the low
concentrations of U in soil. It is well known that microorganisms
and mainly bacteria can reduce and fix uranium in soils. These bac-
teria change soluble U(VI) into highly insoluble complex forming
U(IV) ion, hence stopping chemical leaching (Renshaw et al.,
2005). Microorganisms (bacteria) can reduce the pH of soil in the
anaerobic conditions which enhances the immobilization of U in
soils as the anaerobic conditions may form sulfides ions that form
insoluble uranium sulfides.
6. Conclusions
– The concentrations of U observed in soils collected throughout
the State of Qatar were well within the normal background lev-
els. 235U/238U activity ratios do not indicate DU contamination,
within statistical detectability, anywhere in the country. Varia-
tions in both U concentrations and isotope ratios were statisti-
cally insignificant with respect to presence of DU across Qatar;
therefore no co-locational association could be established with
potential anthropogenic sources of U.
– Development of land use and environmental hotspot maps are
critically essential for continued monitoring of environmental
quality in Qatar. This study has constructed the first maps of
this kind for the country and has established important baseline
data for future studies of this kind. The results did not show that
the distribution of uranium in the topsoil is linked to the
anthropogenic activities and land use.
– Further studies on the occurrence of uranium and its isotopes in
the environment of Qatar should include impacts of air deposi-
tion, transboundary factors and marine systems. Several param-
eters (pH, Fe, Mn, CO3 and bacteria) in the topsoil should be
monitored regularly to identify the link with total uranium con-
tents and different isotopes.
Acknowledgments
This article was made possible by a NPRP Award [08-187-1-
034] from the Qatar National Research Fund (a member of The Qa-
tar Foundation). The statements made herein are solely the respon-
sibility of the authors. The authors would also like to thank Prof.
Jerome Nriagu, Prof. R.D. Schuiling, Prof. Stephanie Handley-Sidhu,
Prof. Anthony Bednar Nora Kuiper and Candace Rowell for their
support to improve the quality of the manuscript. Special thanks
to Prof. Adrian Bath for his constructive, deep and important
comments.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/
j.apgeochem.2013.08.001.
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