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Article history: The uranium concentration and the isotopic ratio 238U/234U have been determined in Cypriot ground-
Received 4 May 2012 water samples by ICP-MS after ultrafiltration and acidification of the samples and a-spectroscopy after
Received in revised form pre-concentration and separation of uranium by cation-exchange (Chelex 100 resin) and electro-
29 August 2012
deposition on stainless steel discs. The uranium concentration in the groundwater samples varies
Accepted 31 October 2012
Available online 26 November 2012
strongly between 0.1 and 40 mg lL1. The highest uranium concentrations are found in groundwater
samples associated with sedimentary rock formations and the obtained isotopic ratio 238U/234U varies
between 0.95 and 1.2 indicating basically the presence of natural uranium in the studied samples. The pH
Keywords:
Uranium
of the groundwater samples is neutral to weak alkaline (7 < pH < 8) and this is attributed to the
Groundwater samples carbonaceous content of the sedimentary rocks and the ophiolitic origin of the igneous rocks, which form
ICP-MS the background geology in Cyprus. Generally, in groundwaters uranium concentration in solution
a-Spectroscopy increases with decreasing pH (7 < pH < 8) and this is attributed to the fact that at lower pH dissolution of
pH soil minerals occurs, and uranium, which is adsorbed or forms solid solution with the geological matrix
EC enters the aqueous phase. This is also corroborated by the strong correlation between the uranium
concentration and the electrical conductivity (e.g. dissolved solids) measured in the groundwaters under
investigation.
Ó 2012 Elsevier Ltd. All rights reserved.
0265-931X/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jenvrad.2012.10.008
188 C. Charalambous et al. / Journal of Environmental Radioactivity 116 (2013) 187e192
2. Materials and methods Groundwater samples were analyzed for total uranium at m/
z ¼ 238 in normal mode (Tune step). The standard operating
Samples were obtained between October and December 2011 conditions used were 1500e1550 W RF Power, 1.05 l min1 carrier
from different Cypriot groundwater systems corresponding basi- gas flow, and 0.1 rps per pump flow rate. The ICP-MS instrument is
cally to igneous and sedimentary rock formations (Fig. 1). A total of fitted with a Micromist glass concentric nebulizer and quartz Scott-
81 samples was collected; 21 out of them correspond to igneous type spray chamber and Agilent CETAC ASX-510 auto sampler.
and 60 to sedimentary groundwater systems. The groundwater Optimization of the ICP-MS was performed daily for total
samples were obtained from already existing groundwater wells, uranium determinations and tuned using a 1 mg l1 tune solution
which are basically used for irrigation purposes. The depth of the (Kit 5185e5959) e Agilent Technologies. Calibration standards (at
wells, generally between 20 and 100 m, corresponds mainly to levels of 0, 0.5, 1, 5, 10, 20, 50 and 100 mg l1 of total U) were
unconfined groundwater systems. Sampling was carried out prepared from a multi-element standard Fluka (Fluka Analytica,
according to the Standard Methods (WHO, 2006). Prior to collection 1000 mg ml1 of U in 1 wt % HNO3) and the correlation coefficient of
for total U analysis, each PTE bottle (1 L) was rinsed 2e3 times with 0.995 for the calibration curve.
the subsequent water sample, to minimize potential elemental
contamination from the bottle during storage. The water was 2.2. a-Spectroscopy
placed unfiltered in a 1 L PTE bottle adding 3 ml HNO3 50% (65%
suprapur, Merck), and transferred immediately to the laboratory for The a-spectroscopic analysis of uranium in selected ground-
analysis. Each sample had a corresponding sampling form with all water samples was performed after pre-concentration and sepa-
relevant information (pumping time, pH, conductivity). During ration of uranium by cation-exchange (Chelex 100 resin) and it’s
field sampling all groundwater samples (for total U analysis) were subsequent electro-deposition on stainless steel discs. The
stored below 8 C using a cool box and on arrival at the laboratory employment of high-resolution a-spectroscopy allows an accurate
were placed in a refrigerator (at <4 C) until sample preparation determination of the activity of the 238U and 234U radioisotopes.
and analysis. pH and EC (electrical conductivity) measurements Generally, 500 ml of each groundwater sample were pre-treated by
were performed using a combined glass- and conductivity elec- cation-exchange as described elsewhere (Pashalidis and Tsertos,
trode, respectively and the uranium analysis was performed by ICP- 2004; Killiari and Pashalidis, 2010). This pre-analytical procedure,
MS and selected samples were investigated also by a-spectroscopy. which is selective for uranium (Killiari and Pashalidis, 2012), was
carried out in parallel for every sample.
Alpha-spectroscopic analysis was performed using a high-
2.1. ICP-MS analysis
resolution a-spectrometer (Alpha Analyst Integrated Alpha Spec-
trometer, Canberra) equipped with semiconductor detectors. Prior to
The analysis for total U in groundwater was performed using the
sample measurement, the background was carefully measured under
EPA Method 200.8 “Analysis of trace and non-trace elements in
identical conditions and was found to be about 5 counts per day
waters and wastes using ICP-MS (Inductively Coupled Plasma Mass
within the energy range of 3e8 MeV. Method calibration using
Spectrometry)” (APHA, 2005). The water samples were analyzed on
cation-exchange separation results in efficiency of 85%. The electro-
an Agilent 7500 CE ICP-MS after microwave digestion at the State
deposition of uranium on stainless steel discs produced results
General Laboratory, Nicosia Cyprus (SGL).
within excellent yields, generally over 99% (Pashalidis and Tsertos,
Suitable analytical reagents, instrument optimization/tuning
2004; Killiari and Pashalidis, 2010). The Minimum Detectable
solution and standards of ultra pure quality were used. Quality
Activity (MDA) reached in the measurements was estimated to be
control validation was undertaken during routine analysis using
about 1 mBq lL1 at the 95% confidence limit. The uncertainty of the
a certified reference material, namely, CRM TM 24.3 (National
uranium activity concentration and the 234/238U ratio are around 10%.
Water Research Institute). Furthermore, U-spiked blanks and
duplicate groundwater samples were analyzed to determine the
3. Results and discussion
accuracy and precision of the method. The validation tests included
determination of trueness (% recovery ¼ 99.4), precision (%
3.1. Uranium levels
RSD ¼ 0.6), limits of detection (LOD ¼ 0.15 mg l1) and quantitation
(LOQ ¼ 0.5 mg l1), and method uncertainty assessment (%U ¼ 2%, at
Sample collection included groundwater samples from different
confidence level 95%). The results were satisfactory and within the
locations in Cyprus corresponding basically to groundwater
accepted validation requirements of the Directive 90/2009/EC.
systems associated with igneous and sedimentary type rock
formations (Fig. 1). The igneous rock formations of the Troodos
mountain range in Cyprus are ophiolites consisting of serpentines,
diabases and pillow lavas. On the other hand, the sedimentary rock
formations are highly retentive rocks such as chalks interbedded
with marls with relatively increased sulfate and magnesium
concentrations, originating exclusively from marine sediments
(Georghiou and Pashalidis, 2007). A typical composition (regarding
main components) of the groundwater samples, which are associ-
ated with sedimentary rocks is given in Table 1.
The data obtained from pH, EC and uranium concentration
measurements are given in Table 2 and the corresponding
descriptive data obtained after statistical treatment are summa-
rized in Table 3 and the uranium concentration in groundwaters
associated with the two different rock types is graphically pre-
sented in the form of a box-plot in Fig. 2. Assuming a student
Fig. 1. Map of Cyprus including sampling points as well as pointing out areas with distribution for the uranium concentration data a comparison of
igneous and sedimentary background lithology. the means at 95% confidence level has been performed. The student
C. Charalambous et al. / Journal of Environmental Radioactivity 116 (2013) 187e192 189
Table 1 Table 3
Chemical analysis (main components) of a Cypriot groundwater in contact with Descriptive parameters obtained after statistical analysis of the data for uranium
sedimentary rock formation and seawater samples. The values given in Table 1 are concentration, pH and conductivity, corresponding to groundwaters related to
average values. igneous and sedimentary rock formations.
Chemical Groundwater Cypriot Seawater Rock formation Number Mean Std Dev Min Median Max
species (mg l1) groundwater (mg l1) [238U] in mg l1
(mg l1) Igneous 21 0.4 0.4 <DL 0.2 1.3
Cl 20 490 325 19,000 Sedimentary 60 3 5 <DL 1.9 39.2
SO2
4 30 260 235 2700 pH
HCO 3 200 408 155 142 Igneous 21 7.9 0.3 7.2 7.9 8.4
Naþ 30 355 250 10,500 Sedimentary 60 7.5 0.4 6.6 7.5 8.7
Mg 2þ
7 75 40 1350 Conductivity in mS cm1
Ca2þ 50 105 85 410 Igneous 21 957 547 296 836 2460
Kþ 3 10 8 390 Sedimentary 60 3212 6408 377 1602 44,000
Boron 0.3 0.6 0.5 4.7
Detection Limit: 0.15 mg l1.
pH 7 7e8 8.2
Quantitation Limit: 0.5 mg l1.
t-test indicates significant difference between the two means and during the island formation. The marine origin of uranium is
hence generally higher uranium levels in groundwaters associated indicated by the main component composition as well as by the
with sedimentary rock formations. The higher uranium concen- relative increased boron concentration in the respective ground-
trations in groundwaters associated with sedimentary rock water systems summarized in Table 1 (Georghiou and Pashalidis,
formations is related to the increased concentration of uranium in 2007).
those rock formations (Tzortzis et al., 2003). On the other hand, the Because there are no rivers that flow across the island the
increased uranium concentration in the sedimentary rock forma- uranium content of the groundwater systems is attributed to the
tions originates from marine uranium, which is most probably left radionuclide inputs from the geological matrix due to rainwater
behind after evaporation of seawater enclosed in those formations infiltration. Specifically rainwater from the rainy period percolates
Table 2
238/234
Uranium concentration and U isotopic ratio corresponding to groundwaters related to igneous (i) and sedimentary (s) rock formations.
4. Conclusions
concentration varies between 0.1 and 40 mg lL1. Generally, sedi- Bruno, J., Wersin, P., Stumm, W., 1992. On the influence of carbonate in mineral
dissolution: II. The solubility of FeCO3(s) at 25 C and 1 atm total pressure.
mentary rock formations in Cyprus contain higher uranium levels
Geochim. et Cosmochim. Acta 56, 1149e1155.
and hence the corresponding groundwaters are characterized by Chau, N.D., Michalec, B., 2009. Natural radioactivity in bottled natural spring,
higher uranium concentrations. Among the studied systems, mineral and therapeutic waters in Poland. J. Radioanal. Nucl. Chem. 279, 121e
there is only one groundwater with uranium concentration above 129.
Desideri, D., Roselli, C., Feduzi, L., Meli, M.A., 2007. Radiological characterization of
the limit proposed by WHO for drinking water. drinking water in Central Italy. J. Environ. Radioact. 87, 13e19.
238 234
U/ U isotopic ratios clearly show that uranium in the Georghiou, G., Pashalidis, I., 2007. Boron in ground waters of Nicosia (Cyprus) and
studied waters is of natural origin. Moreover, increased its treatment by reverse osmosis. Desalination 215, 104e110.
238 234 Ioannidou, A., Samaropoulos, I., Efstathiou, M., Pashalidis, I., 2011. Uranium in
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old-type waters. On the other hand, low uranium activity Ivanovich, M., Harmon, R.S., 1992. Uranium-series Disequilibrium: Applications to
Earth, Marine and Environmental Sciences. Clarendon Press, Oxford, p. 910.
concentrations and 238U/234U isotopic ratios found in ground- Killiari, T., Pashalidis, I., 2010. Simplified alpha-spectroscopic analysis of uranium in
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presence of relatively younger waters. 968.
Killiari, T., Pashalidis, I., 2012. Selective separation of actinyl(V, VI) cations from
Positive correlation between uranium concentration and elec-
aqueous solutions by Chelex-100. Radiochim. Acta 100, 439e443.
trical conductivity measured in the groundwaters under inves- Pashalidis, I., Tsertos, H., 2004. Radiometric determination of uranium in natural
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techniques. J. Radioanal. Nucl. Chem. 260, 439e442.
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Pashalidis, I., Czerwinski, K.R., Fanghaenel, Th., Kim, J.I., 1997. A study of solid-Liquid
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