ARTICLE IN PRESS

Applied Radiation and Isotopes 61 (2004) 319323

Low-level measurements of tritium in water

! b M. Villaa,*, G. Manjon
! Departamento de F! sica Atomica, Molecular y Nuclear, Facultad de F! sica, Universidad de Sevilla, Av. Reina Mercedes s/n, E41080 Sevilla, Spain b Departamento de F! sica Aplicada II, E.T.S. Arquitectura, Universidad de Sevilla, Av. Reina Mercedes 2, E41012 Sevilla, Spain
a

Abstract Using a liquid scintillation counter, an experimental procedure for measuring low-level activity concentrations of tritium in environmental water has been developed by our laboratory, using the electrolytic tritium enrichment. Additionally, some quality tests were applied in order to assure the goodness of the method. Well-known water samples collected in the Tagus River (West of Spain) and the Danube River (Bulgaria), both affected by nuclear plant releases, were analysed and results were compared to previous data. The analytical procedure was applied to drinking water samples from the public water supply of Seville and mineral waters from different springs in Spain in order to characterize its origin. Due to the very low levels of tritium in the analysed samples, some results were reported as lower than the minimum detectable activity concentration (MDA). However, the count rate of these measurements was over the background count rate of LS counter in all the cases. For that reason, an exhaustive discussion about the meaning of the MDA, using an experimental essay, was made in order to establish a rigorous criterion that leads to a reliable value in the case of low-level measurements. r 2004 Elsevier Ltd. All rights reserved.
Keywords: Tritium levels; Water; Detection limit; Critical level

Introduction Natural levels of 3H in environmental samples, mainly due to interactions of the cosmic rays with the atmosphere, were enhanced by the atmospheric nuclear test conducted from 1945 until 1963. Since 1963, the stop of atmospheric nuclear weapon tests the released activity of 3 H has decayed, with a half-life of 12.33 yr, in the atmosphere (UNSCEAR, 1982). Nowadays, the levels of tritium in the atmosphere are those of natural origin before the nuclear tests. Furthermore, nuclear power plants (NPP), for both civilian and military uses of nuclear energy, have become a signicant source of tritium in the environment. These facilities release tritium mostly into the close surface waters and therefore the global distribution of tritium is not uniform. Thus, a local radioactive impact can be
*Corresponding author. Tel.: +34-95-4550924; fax: +34-954554445. E-mail address: mvilla@us.es (M. Villa).

observed in the vicinity of Nuclear Power Plants, where the tritium activity concentration in waters might be over the natural levels. The purpose of this work was to establish a rigorous method to measure low-levels of tritium in natural water samples, as well as waters affected by nuclear power plants. Analyses of river water samples collected around NPPs were done. Results were compared to the values established by other laboratories. In addition, we have developed a method for electrolytic enrichment of tritium. Finally, the method was applied to drinking water, commercial mineral waters and rainwater samples, where low activity concentrations of tritium were expected. All the results were obtained over the background, however, the activity levels in some samples were close to the Critical Level (Currie, 1968). For that reason, an additional essay was made in order to establish a threshold level in order to determine the activity in samples with very low count rates just over the background count rate.

0969-8043/$ - see front matter r 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.apradiso.2004.03.027

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320 ! / Applied Radiation and Isotopes 61 (2004) 319323 M. Villa, G. Manjon

2. Experimental procedure 2.1. Sampling Different types of water samples were involved in this work. Rainwater samples were collected using a 1 m2 conic stainless steel funnel. The tap water was taken directly from the public water supply of Seville (EMASESATM). Mineral waters from different springs in Spain are commercially available (Zambra, Fontvella, ! n de Cabras). Finally, Lanjaron, Fuente Primavera, Sola river waters were provided by other laboratories. The samples collected in the Tagus River (Spain), were provided by Dr. Baeza (Universidad de Extremadura) and the samples collected in the Danube River (Bulgaria) were supplied by Mrs. Abramova (Kozloduy NPP). 2.2. Sample treatment and measurement The samples that were measured without enrichment were previously distilled and then mixed with the scintillation cocktail Optiphase Hisafe3. The electrolytic concentration of tritium was made following the procedure and the cells design described by Baeza (Baeza et al., 1999) with slight variations. The cells we have used have cylindrical geometry with stainless electrodes. Each electrolytic run comprises 1 blank, 3 reference dilutions of tritiated water and 6 samples for measurement. The dead water (free of tritium) used as blank is provided by Dr. Trilla from the ! de 3H y de 14C (Universidad Servicio de Datacion ! Autonoma de Barcelona). An ultra-low-background Wallac Quantulus 1220 liquid scintillation spectrometer has been used for the tritium measurements. For an electrolyticly concentrated sample, Taylor (1977) suggests the relationship  P Wf Ci ; 1 Cf Wi where Ci/Cf are the initial/nal 3H concentration in the electrolyte. Wi and Wf are, respectively, the masses of the electrolysed sample before and after the electrolytic enrichment. P is the enrichment parameter, and is assumed to be constant for all the cells in every electrolytic run. It is determined from the cells containing traced samples. Thus, activity concentration A (Bq/l) for an electrolyzed sample is deduced as Rs Rb ln2te =T1=2 1 A e 2 P ; e V 60 Wsi =Wsf where Rs is the net count rate (cpm) of the electrolysed sample and Wsi and Wsf are, respectively, the masses of the sample before and after the enrichment. V (l) is the

volume of the sample contained in the counting vial, te (years) is the time elapsed between the collection and the measurement of the sample, T1/2 is the tritium half-life (12.3 years) and e is the counting efciency. The tritium counting efciency e is determined with the measurement of tritium standard sources. According to Currie (1968), the Detection Limit LD is dened as p 2:71 4:65 Rb t LD ; 3 t where t is the measurement time of the background sample that coincide with the measurement time of the sample. LD is expressed in cpm, although it is very common to give units to this value to obtain the Minimum Detectable Activity, which can be directly compared to the activity concentration of a sample. Thus, for non electrolysed and electrolysed samples it is dened as p 2:71 4:65 Rb t MDA ; 4 eV 60t p 2:71 4:65 Rb t 1 5 MDA P : eV 60t Wsi =Wsf The Critical Level dened by Currie (1968) is the one used to establish whether or not a measurement is over the background. The formula for the Critical Level, also called Decision Limit, is. r 2Rb LC 1:64 : 6 t The criterion is the following. If RsRb > LC, with a probability of error of 5%, the registered pulses include a contribution by the sample. In that case we calculate the tritium activity in the sample.

3. Results and discussion 3.1. Study of Curries critical level It is usually found in the bibliography, that the Minimum Detectable Activity is used to discriminate a measurement from the background. According to Currie, it must be the Critical Level LC, and not the LD, or the equivalent MDA, the discrimination threshold. In the water samples analysed up to now, we have observed that the counting rate in this samples is very close to the background rate. In addition, the natural activity present in the sample is so small that is close or lower to the Minimum Detectable Activity of the technique. For these reasons, the discrimination of the tritium activity from background in these cases is not a trivial problem.

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! / Applied Radiation and Isotopes 61 (2004) 319323 M. Villa, G. Manjon 321 Table 1 Tritium activity concentration for traced samples measured after an electrolytic processes Being Am the measured activity and At the true activity of the tritiated water Critical Level (LC) and Minimum Detectable Activity (MDA) of the samples and Curries discrimination criterion Sample 1 2 3 4 5 6 7 8 9 Am (Bq/l) 0,84 0,72 0,68 0,33 0,20 0,19 0,18 0,13 0,08 7s 0,11 0,07 0,06 0,05 0,05 0,07 0,08 0,08 0,07 At (Bq/l) 0,90 0,60 0,51 0,34 0,25 0,23 0,24 0,27 0,18 7s 0,04 0,02 0,03 0,01 0,01 0,01 0,01 0,01 0,01 LC (cpm) 0,085 0,087 0,087 0,087 0,087 0,086 0,087 0,085 0,086 (RsRb) >LC Yes Yes Yes Yes Yes Yes Yes No No MDA (Bq/l) 0,29 0,14 0,14 0,16 0,14 0,22 0,24 0,26 0,24

Thus, it must be established if Curries discrimination criterion can be applied to tritium measurements of very low activity concentration. For that purpose, we have made a set of electrolytic tritium concentrations using diluted tritiated water samples of known activity; the samples were traced with small amounts of tritium and then concentrated electrolytically, we calculate their activity in the usual way. Afterwards, we have compared the true activity with the results obtained using the electrolytic enrichment, the values are shown in Table 1. The measurement of samples 13 gives counting rates which are over the background and the activity measured, although low, is appreciably higher than the MDA. Furthermore, the activity measured is in coincidence, within the error, with the true activity of the tritiated water. In two cases, samples 8 and 9, RsRb is below LC. Specically, sample 8 gives a positive result for the tritium activity, however, the measured activity is not in agreement with the true activity of the sample. This result stands out the importance of LC to discriminate a true result from a background measurement. For the rest of the samples, RsRb is higher than LC. In addition, in samples 6 and 7 the results of the activity are below the MDA. However, within the error, in all the samples where RsRb > LC, the activities measured are in agreement with the true activity of the traced samples. This result conrm that the Minimum Detectable Activity is an a priori limit that does not indicate whether or not a measurement is a background result. Thus, it is possible to present an accurate activity of a sample which is below the MDA. On the other hand, we have veried that if the counting rate does not exceed the Critical Limit LC, the result of the activity concentration in this samples is not reliable and do not has to be considered. 3.2. Riverwater samples around nuclear power plants The radioactive impact of two NPP, both equipped with a pressure water reactor (PWR), can be compared

by measuring the activity concentration of 3H in the riverwater used as coolant, which is opened to the close environment. For that reason, high 3H levels are expected in these samples. In this work, the selected NPP were Almaraz (West of Spain), which is located in the bank of Tagus River, and Kozloduy (Bulgaria), which is located in the bank of Danube River. Table 2 presents the activity concentration of 3H in the Tagus River, obtained without electrolytic enrichment. Table 3 presents the activity concentrations of 3H in the Danube River. The levels observed in the Tagus River were an order of magnitude higher than the ones observed in the Danube River. Then, a higher radioactive impact by Almaraz NPP in the Tagus River can be inferred. The direct measurement of tritiated water samples is checked comparing our results in Tagus river to previous data obtained by Dr. Baeza in the same samples (Table 2). Both measurements coincide within the error, conrming the goodness of the procedure. Furthermore, our results have been conrmed in an intercomparison procedure, concerning to the Tajo River water samples. In this intercomparison were included the measures reported by 12 laboratories from Portugal and Spain. The average activity of all the measures, excluding the results of two outliers, was 9579 Bq/l. Our laboratory has obtained 10375 Bq/l, which is a result within the incertitude. The electrolytic enrichment step was veried in the Danube River samples (Table 3), the same sample were measured twice, without any enrichment procedure and using the electrolytic enrichment technique. The activity of the sample from upstream Danube, non affected by Kozloduy NPP, is below the Critical Level if no enrichment method is used. The electrolytic concentration diminishes the MDA an order of magnitude, thus, the activity concentration for that sample is 1.7 Bq/l. The results with and without enrichment are in agreement, within the incertitude, for the three recollected samples.

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322 ! / Applied Radiation and Isotopes 61 (2004) 319323 M. Villa, G. Manjon Table 2 Tritium activity concentration in samples from the Tagus river. Sampling location Downstream (60 Km) Downstream (60 Km) Downstream (40 Km) Downstream (1 Km) Downstream (1 Km) Outlet/cooling reservoir Outlet/cooling reservoir Collecting date 01-07-01 01-09-01 01-11-01 01-07-01 01-10-01 01-11-01 01-12-01 U. Sevilla A (Bq/l) 15 19 17 121 36 271 251 7s 1 1 1 6 2 12 11 MDA Bq/l 1,8 U. Extremadura A (Bq/l) 15 20 21 123 36 271 251 7s 2 2 6 2 2 13 12

The results correspond to the measurements carried over by the University of Sevilla and the University of Extremadura. Table 3 Tritum activity concentration in samples from the Danube river. Sampling location Downstream Upstream Outlet 01-01-03 Collecting date Without electrolysis A (Bq/l) 2,0 Not detected 10,3 7s 0,4 1,5 MDA (Bq/l) 1,9 With electrolysis A (Bq/l) 3,0 1,7 10,7 7s 0,2 0,1 0,7 MDA (Bq/l) 0,2

The results were obtained without any enrichment processes and with electrolytic enrichment.

3.3. Mineral water samples Table 4 presents the activity concentration of 3H in commercial mineral waters. In this case, the application of the electrolytic enrichment is always necessary. However the results were under the LC, in two cases: ! n de Cabras. The springs of Fuente Primavera and Sola those does not receive any supply from the exterior, for !n that reason, in the waters Fuente Primavera and Sola de Cabras the natural tritium would have decayed. ! n de Cabras spring has been Actually, water from Sola checked to be used as a blank for the electrolytic processes. So, the tritium electrolytic enrichment proce! n de Cabras dure was applied to six aliquots of Sola water and the count rates obtained were compared to the results obtained with a background sample. The average values for the six aliquots and the background sample are, respectively, 1.08 and 1.10, with a standard deviations of 0.04 and 0.03. This values are equivalent within the error. Conrming the availability of Solan de Cabras spring water as a blank simple. 3.4. Other samples The low limit of detection obtained with this tritium enrichment method make possible to measure the activity concentration of 3H in othersamples, like rainwater or tapwater. Thus, Table 4 presents some results of 3H in rainwater samples collected in Seville since November 2001.

Table 4 Tritium activity in mineral waters from several springs in Spain, tap and rain water and minimum detectable activity. Origin Zambra Fontvella ! Lanjaron Fuente Primavera ! n de Cabras Sola Tap water Collecting date May-02 Jul-02 Sep-02 Oct-02 Mar-03 May-03 Nov-01 Mar-02 Mar-02 Apr-02 Apr-02 Nov-02 A (Bq/l) 0,28 0,55 0,46 Not detected Not detected 0,47 0,15 0,32 0,31 0,21 0,26 0,32 0,37 0,16 0,19 0,13 0,14 7s 0,08 0,08 0,07 MDA (Bq/l) 0,23 0,20 0,19 0,20 0,21 0,45 0,20 0,15 0,21 0,23 0,21 0,22 0,28 0,22 0,51 0,20 0,18

0,05 0,04 0,03 0,07 0,07 0,07 0,08 0,10 0,07 0,16 0,13 0,07

Rainwater

All the measurements where done using the electrolytic concentration method.

Water public supply network (EMASESA) is usually monitored by our laboratory as a participant in REVIRA-REM, a radiological surveillance coordinated

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by Spanish Consejo de Seguridad Nuclear. The presence of 3H in these samples must be well established. Some results in samples collected in 2002 and 2003 are listed in Table 4. In both tables, the results are presented despite that sometimes they are lower than the MDA. In all the measurements carried over with rain and tap water, the results were over LC.

river samples affected by NPP releases, but also natural levels of tritium in mineral, tap and rainwater.

References
Currie, L.A., 1968. Limits for qualitative detection and quantitative determination. Anal. Chem. 40 (3), 586593. ! C., 1999. A procedure for the Baeza, A., Garc! a, E., Miro, determination of very low activity levels of tritium in water samples. J. Radioanal. Nucl. Chem. 241 (1), 93100. Taylor, C.B., 1977. Tritium enrichment of environmental water by electrolysis. Procedings of the International Conference of Low-Radioactivity Measurements and Applications. Bratislava, Slovenske pedagogicke nakladatielstvo, pp. 131-140. UNSCEAR, 1982. Sources and effects of ionizing radiation: sources and biological effects, 1982. Report to the General Assembly, with Annexes, United Scientic Committee on the Effects of Atomic Radiation. UN, New York, 1993.

4. Conclusions We have developed an electrolytic enrichment method to measure low-level tritium concentrations. We have tested Curries discrimination levels to be used in measurements with very low contents of tritium, the activity concentrations obtained when the counting rate is over the Critical Level are reliable within the incertitude. Thus, we manage to measure successfully