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Journal of Environmental Radioactivity 116 (2013) 187e192

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Journal of Environmental Radioactivity


journal homepage: www.elsevier.com/locate/jenvrad

Uranium levels in Cypriot groundwater samples determined by ICP-MS


and a-spectroscopy
Chrystalla Charalambous a, Maria Aletrari a, Panagiota Piera a, Popi Nicolaidou-Kanari a,
Maria Efstathiou b, Ioannis Pashalidis b, *
a
State General Laboratory, Ministry of Health, 44 Kimonos Str., Cy-1451 Nicosia, Cyprus
b
Department of Chemistry, University of Cyprus, P.O. Box 20537, Cy-1678 Nicosia, Cyprus

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

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.

1. Introduction carried out in different places in order to study the uranium


concentrations in natural hot spring waters, spa waters and
Uranium is a ubiquitous, primordial radionuclide, the concen- drinking waters (Pashalidis and Tsertos, 2004; Ioannidou et al.,
tration of which in the environment strongly depends on the 2011; Chau and Michalec, 2009). Furthermore, knowledge of
geological matrix and varies between 0.1 and 500 ppm. Uranium in uranium isotopic ratios in natural systems is of particular interest
waters results from the weathering of rocks and soil. In ground- regarding geochronology and pollution budgets (Ivanovich and
waters, the nuclide activities are governed by a number of Harmon, 1992).
processes, including dissolution and adsorptionedesorption In the present study uranium concentrations and the 238U/234U
processes. Resulting isotopic fractionation of the element, which isotopic ratios have been determined in Cypriot groundwater
is unique among the heavy elements, and has been useful in systems, corresponding mainly to igneous and sedimentary rock
identifying waters, tracing them in the hydrologic cycle and esti- formations. The analysis was performed by ICP-MS and a-spec-
mating mixing ratios when surface waters merge. (Porcelli and troscopy and the uranium concentration has been correlated to pH
Swarzenski, 2003). and electrical conductivity (EC) of the solutions. This study repre-
Knowledge of the uranium concentration in ground and surface sents a comprehensive investigation on uranium levels in Cypriot
waters is important in performing radiological impact assessment groundwater systems, which are used basically for irrigation
of various anthropogenic activities and aims to secure the increased purposes and eventually as drinking water resources, and aims to
standard of life in modern societies. A number of studies has been provide background values for uranium, a database for radiological
impact assessment, point out the differences between different
* Corresponding author. types of waters and provide an evaluation of the variation of
E-mail address: pspasch@ucy.ac.cy (I. Pashalidis). uranium levels in the studied groundwater systems.

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.

Nr Rock type [U]/(mg l1) 234/238


U pH EC (mS cm1) Nr Rock type [U]/(mg l1) 234/238
U pH EC (mS cm1)
1 i 0.25 0.9 7.4 1185 42 s 0.37 1.0 8.2 954
2 i 0.23 0.9 8.2 836 43 s 2.79 1.2 7.3 2900
3 i 0.15 1.0 7.8 1272 44 s 0.28 0.9 7.5 1031
4 i 1.26 1.2 8.2 750 45 s 1.02 1.1 7.9 2230
5 i 1.34 1.0 8.0 1024 46 s 3.19 1.3 7.8 1523
6 i 0.11 1.1 7.4 426 47 s 1.32 1.0 7.3 3300
7 i 0.1 0.9 8.3 542 48 s 3.18 1.2 7.7 840
8 i 1.11 0.9 7.7 1823 49 s 4.29 1.4 7.1 5220
9 i 0.11 1.1 7.9 591 50 s 7.24 1.5 7.0 1843
10 i 0.12 1.4 7.9 1044 51 s 4.47 1.3 6.9 44,000
11 i 0.20 1.1 7.9 326 52 s 3.20 1.2 7.1 1921
12 i 0.53 0.9 7.7 928 53 s 0.91 1.0 7.8 892
13 i 0.79 1.0 7.9 2460 54 s 1.30 1.1 7.8 1601
14 i 0.3 1.1 8.4 1350 55 s 11.28 1.5 6.9 3870
15 i 0.33 0.9 7.2 745 56 s 1.90 1.1 7.0 841
16 i 0.15 0.9 8.2 296 57 s 1.22 1.1 7.5 1278
17 i 0.15 1.0 7.7 1786 58 s 0.34 0.9 7.9 1603
18 i 0.15 0.9 8.0 591 59 s 2.31 1.3 7.3 793
19 i 0.15 1.0 7.8 436 60 s 2.73 1.3 7.5 1160
20 i 0.15 0.9 8.0 810 61 s 0.15 0.9 8.0 377
21 i 0.15 1.0 8.0 873 62 s 6.32 1.4 7.5 2060
22 s 1.28 1.3 8.0 1946 63 s 1.40 1.1 7.5 1429
23 s 6.65 1.5 7.0 4200 64 s 6.62 1.5 6.9 23,200
24 s 0.91 0.8 7.4 2970 65 s 1.13 1.0 7.3 16,610
25 s 1.89 0.9 7.4 1525 66 s 1.94 1.1 7.9 1862
26 s 0.85 0.9 7.9 910 67 s 2.68 1.2 7.9 2140
27 s 3.06 1.3 7.5 1713 68 s 6.48 1.4 7.4 3010
28 s 3.57 1.5 7.4 1643 69 s 3.92 1.2 7.6 1715
29 s 1.22 1.1 7.7 995 70 s 4.11 1.3 7.2 1856
30 s 1.97 1.0 7.8 1144 71 s 1.88 1.1 7.6 1246
31 s 2.23 1.2 7.6 1469 72 s 0.38 0.9 7.5 1008
32 s 0.82 1.1 8.0 802 73 s 39.16 1.5 7.1 6270
33 s 0.87 1.0 7.7 887 74 s 2.93 1.2 7.5 4160
34 s 2.78 1.1 6.6 3190 75 s 0.62 1.0 8.7 947
35 s 3.77 1.3 6.8 1750 76 s 0.15 0.9 8.2 1013
36 s 4.42 1.4 7.3 2940 77 s 2.52 1.2 7.3 4310
37 s 2.09 1.2 6.9 3030 78 s 0.52 0.9 7.4 1030
38 s 0.12 1.0 7.7 1252 79 s 0.91 0.9 7.3 1043
39 s 0.10 0.9 8.1 765 80 s 1.95 1.1 7.5 1336
40 s 0.18 0.9 7.8 1196 81 s 0.15 0.9 7.2 2880
41 s 0.72 0.9 8.2 1092
190 C. Charalambous et al. / Journal of Environmental Radioactivity 116 (2013) 187e192

Fig. 4. 238U/234U activity ratio values determined in groundwaters associated with


Fig. 2. Box-plot of uranium concentration in groundwaters associated with igneous igneous and sedimentary rock formations. Each box encloses 50% of the data within
and sedimentary rock formations. Each box encloses 50% of the data within a group e.g. a group e.g. the ends of the box are the 25th and the 75th quantiles. The line across the
the ends of the box are the 25th and the 75th quantiles. The line across the box box identifies the median value and the lines, that extent from each end of the box,
identifies the median value and the lines, that extent from each end of the box, identify identify a calculated range which includes the outermost data of a group.
a calculated range which includes the outermost data of a group.
two isotopes 234U and 238U occurs because of radioactive decay and
the resulting radiochemical reactions. In fact, 234U recoil resulting
through the top-soil and rock formations hosting the groundwater
in crystal damage and leaching are the main mechanisms for the
system, dissolves and becomes enriched in dissolved solids and 238 234
U/ U disequilibrium in groundwater (Porcelli and Swarzenski,
uranium that finally enter the groundwater system. The impact of
2003; Ivanovich and Harmon, 1992). The determination of the
airborne radioactivity is expected to be insignificant due to rela- 238 234
U/ U ratio in disequilibrium is of importance in understanding
tively low uranium concentration in rainwater. In addition, possible
hydrological, geochemical and chemical processes in terrestrial
contamination of the groundwater system by anthropogenic sour-
studies. The observed disequilibrium in the studied samples is
ces can be excluded because of the absence of any human activities
correlated with the different geological formations, e.g. igneous
that could lead to uranium contamination in the area as well as the
and sedimentary rock formations and the highest 238U/234U ratio
a-spectroscopic analysis of representative samples, which clearly values indicate most probably old-type waters. On the other hand,
shows that the a-radioactivity in the studied samples is related
groundwaters corresponding to igneous rock formations with
basically to natural uranium (Fig. 3). The two main a-peaks due to
relatively low uranium activity concentrations and 238U/234U
the 238U and 234U radioisotopes with energies of 4.198 and
isotopic ratios, point to the presence of younger waters with
4.776 MeV, respectively are clearly shown. The small contribution
a stronger contribution of a local recharge component to the
of the 235U radioisotope (below the experimental detection limit)
groundwater. However, further studies are required to establish the
does not give a statistically significant a-peak.
relationship between the disequilibrium activity ratio and the
The 238U/234U ratio values for the two different types of
source of uranium in the water.
groundwaters are shown graphically as box-plots in Fig. 4.
From the radiological point of view none of the groundwater
According to Fig. 4 the 238U/234U ratio values vary between 0.9 and
samples exceeds the suggested limits by WHO and EU (WHO, 2006;
1.5 and the higher values correspond generally to groundwaters
Desideri et al., 2007) for alpha radioactivity in drinking water,
associated with sedimentary rock formations. In naturally occur-
which is 0.5 Bq l1. Regarding the chemotoxic effects, the guidance
ring uranium radioisotopes, the activity ratio 238U/234U is usually
level for uranium in drinking water is 15 mg l1 natural uranium
about 1.05. The radioactive disequilibrium observed between the
which corresponds to 0.19 Bq l1 238U radioactivity concentration.
Among the studied groundwater samples, only one sample exceeds
the limit suggested by WHO (2006) for the uranium concentration
in drinking water. Although using these groundwaters for human
consumption isn’t recommended, their utilization for irrigation
purposes wouldn’t imply any excessive (radio)toxic exposure to
population.

3.2. Correlation of the uranium concentration with pH and EC

Fig. 5 presents graphically a correlation between the uranium


concentration ([U]) and the corresponding pH values in the studied
waters and in the pH range between 7 and 8. The dotted lines are
obtained by linear regression of the experimental data and related
statistical parameters (e.g. correlation coefficient (R) and proba-
bility (p)) are: Ri ¼ 0.07 and pi > 0.77 and, Rs ¼ 0.37, p < 0.006 for
the values of [U] in groundwaters associated with igneous and
sedimentary rock formations, respectively. According to the
Fig. 3. A characteristic uranium a-spectrum of a Cypriot groundwater sample. statistical evaluation there is no correlation between pH and [U] for
C. Charalambous et al. / Journal of Environmental Radioactivity 116 (2013) 187e192 191

Fig. 8. Correlation between uranium concentration in groundwater samples corre-


Fig. 5. Correlation between uranium concentration in groundwater samples corre- sponding to igneous and sedimentary rock formations, and electrical conductivity (e.g.
sponding to igneous and sedimentary rock formations and solution pH. dissolved solids) of the solution.

(Pashalidis et al., 1997). However, the uranium concentration in the


respective waters is far below the solubility limit and depends only
on the uranium amount dissolved from the corresponding
geological matrix. Generally, decreasing pH results in the dissolu-
tion of soil minerals (Bruno et al., 1992) and because uranium is
adsorbed or forms solid solution with the soil mineral particles
enters the aqueous phase upon mineral dissolution. Hence,
decreasing pH results in increasing uranium concentration in
solution. This effect can be explained by the carbonaceous solid
phase dissolution as is schematically depicted in Fig. 6.
Fig. 6. Schematic illustration of the pH-dependent dissolution of a calcareous sedi- Fig. 7 shows the electrical conductivity (EC in mS cm1), which
ment and release of its uranium content into solution. corresponds to the total dissolved solids in the respective waters, as
a function of pH. Linear regression of the corresponding experi-
the groundwaters related to igneous rocks and this can be most mental data reveals that EC of the groundwaters related to sedi-
probably attributed to the relatively low pH-dependent solubility of mentary rocks decreases generally with increasing pH (Rs ¼ 0.55,
the respective rocks and their relatively low [U]. However, there is ps < 0.0001). This effect can be attributed to the dissolution of
a statistically significant correlation between [U] and pH for carbonaceous and soil minerals, which dissolution depends
groundwaters associated with sedimentary rock formations, indi- strongly on the pH and carbonate concentration in solution (Bruno
cating that uranium concentration in the studied waters decreases et al., 1992). However, this trend is weak (Ri ¼ 0.11, pi > 0.64) for
with increasing pH. This seems to be in contradiction with results groundwaters related to igneous rocks and can be attributed to the
obtained from uranium solubility experiments, which show an lower solubility of the igneous rocks and to their relatively low
increase in uranium solubility for pH > 6, because of the formation uranium content.
L 2)L The dependence of the uranium levels determined in ground-
of very stable carbonate complexes (e.g. UO2(CO3)(2n n )
waters waters from the amount of solids dissolved (e.g. dissolution
of the geological matrix) is corroborated by the correlation of the
uranium concentration ([U]) with the electrical conductivity (EC)
measured in the groundwaters under investigation (Fig. 8). The
data in Fig. 8 have been fitted by linear regression and the corre-
sponding statistical parameters are: Ri ¼ 0.39 and pi > 0.08, and
Rs ¼ 0.54 and ps < 0.0001 for groundwaters related to igneous and
sedimentary rock formations, respectively. This data reveal a rela-
tively good linear correlation between [U] and EC, particularly for
waters related to sedimentary rock formations and indicate that
generally uranium concentration in solution increases with
increasing electrical conductivity or total dissolved solids in
a groundwater system.

4. Conclusions

The results obtained from this study lead to the following


conclusions:
Fig. 7. Correlation between electrical conductivity (e.g. dissolved solids) of the
groundwater samples corresponding to igneous and sedimentary rock formations and Uranium concentrations in Cypriot groundwater samples depend
solution pH. on the rock formations, which are hosting the groundwater. The
192 C. Charalambous et al. / Journal of Environmental Radioactivity 116 (2013) 187e192

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