Journal of Radioanalytical and Nuclear Chemistry, Vol. 269, No.

2 (2006) 397–401

Standardized methods for measuring radionuclides in drinking water

M. Forte,1* A. Bertolo,2 F. D’Alberti,3 P. De Felice,3 D. Desideri,4 M. Esposito,5 R. Fresca Fantoni,6
R. Lorenzelli,7 A. Luciani,8 M. Magnoni,9 F. Marsili,10 A. Moretti,11 G. Queirazza,12 S. Risica,13
R. Rusconi,1 S. Sandri,14 R. Trevisi,15 M. T. Valentini Ganzerli16
1 ARPA Lombardia, via Juvara 22, 20129 Milano, Italy
2 ARPA Veneto, via Ospedale 22, 35100 Padova, Italy
3 EC, JRC – TP 21020 Ispra, Varese, Italy
4 Università di Urbino, P.zza Risorgimento 6, 61029 Urbino, Italy
5 U-Series srl, via Fanin 48, 40127 Bologna, Italy
6 ENI–AGIP, via Emilia 1, 20097 S. Donato M.se, Milano, Italy
7 ENEA, 40032 Camugnano, Bologna, Italy
8 ENEA, via dei Colli 16, 40136 Bologna, Italy
9 ARPA Piemonte, via Jervis 30, 10015 Ivrea, Torino, Italy
10 ENEA, CP 2400, 00100 Roma, Italy
11 Università dell’Aquila, 67010 Camugnano, L’Aquila, Italy
12 Università di Pavia, Via Montefiascone 25, 27100 Pavia, Italy
13 Istituto Superiore di Sanità, V.le Regina Elena 299, 00161 Roma, Italy
14 ENEA, via Fermi 45, 00044 Frascati, Roma, Italy
15 ISPESL, via Fontana Candida 1, 00040 M.P. Catone, Roma, Italy
16 Università di Pavia, V.le Taramelli 12, 27100 Pavia, Italy

(Received April 6, 2006)

In 2002 the Italian Standardisation Organisation (UNI) – Nuclear Energy Commission (UNICEN) – appointed a working group with the main task
of writing a set of standards on drinking water measurements. To date two standards have been designed, namely, for total alpha- and beta-activity,
and 222Rn. Further procedures are under development for measuring 226Ra and U isotopes, and gamma-emitting radionuclides in water. The paper
gives an overview of these standards, both developed and under study, with special attention to the validation of the methods.

Introduction Organisation (UNI) has produced a series of standards in

The World Health Organisation (WHO) and the US
Environmental Protection Agency (EPA) have issued
several regulations on drinking water (the most recent
ones are listed as references).1,2 However, only by the
end of the 1990’s did the Council of the European Union
issue its first regulation specifically limiting
radionuclides in drinking water. The implementation of
the existing EU Basic Safety Standards for the
protection from ionizing radiation3 was deemed to
provide sufficient protection for the population from
exposure to radionuclides in drinking water. The
98/83/EC Directive,4 which requires the control of
radioactivity levels in water for human consumption,
was then followed by the European Commission
Recommendation5 concerning the radiological quality of
drinking water supplies regarding radon and long-lived
radon decay products. EC recommendations do not force
any obligation onto Member States, whereas directives
must be transposed into national laws by Member States.
These regulations in Europe were a starting point for a
new awareness of, and interest in, the potential content
of radionuclides in drinking water, related measurement
techniques and normative standards. In Italy, during the
last two decades, the Italian Standardisation
the field of environmental radioactivity measurements,
life sciences and radioecology. In 2002, a new working
group was appointed within the Nuclear Energy
Commission (UNICEN), with the main task of writing a
new set of standards on drinking water measurements.
The effort seemed worthwhile given the scarcity of
available normative standards in the field. Experts from
several regional laboratories, national research bodies
and universities participated in the working group
actions.
Experimental
Measurement methods
The working group started by examining the existing
documents produced by the International
Standardization Organization (ISO). Two of these
standards, ISO 9696 and ISO 9697,6,7 address gross
alpha- and beta-activity measurements, respectively, in
non-saline water by the thick source method and are
currently under revision. A third standard, ISO 9698,8
concerns the determination of tritium by liquid
scintillation counting (LSC), and has been confirmed.

* E-mail: m.forte@arpalombardia.it

0236–5731/USD 20.00 Akadémiai Kiadó, Budapest

© 2006 Akadémiai Kiadó, Budapest Springer, Dordrecht
 M. FORTE et al.: STANDARDIZED METHODS FOR MEASURING RADIONUCLIDES IN DRINKING WATER
The latter document was translated into Italian as a UNI-
ISO standard, and its updating will account for any
relevant technical development in measuring
instrumentation.
The measurement method considered in the ISO
9696 and ISO 9697 standards is both effort and time
consuming, but widely applied with the required
sensitivity that meets the above-mentioned regulatory
requirements.1 Additionally, the measurement
instrumentation required is widely available at a
reasonable cost. Once approved, these standards will be
incorporated by UNI-ISO.
Along with these activities, and on the basis of the
acquired expertise, the working group has started the
design of a new set of documents on widely used
measuring methods. These documents concern
experimental methods in current usage, but not yet
regulated by existing standards, which use LSC for total
alpha- and beta-radioactivity and for radon-in-water
measurements. The approach followed for the writing of
new standards entails the direct involvement of all
working group participants: members contribute their
own experience and take into consideration the most
updated literature on the subjects. In several cases the
quality system procedures of participating laboratories
were used as the basis for developing new standards.
They are briefly discussed in the following paragraphs.
Gross alpha- and beta-activity measurement
In consideration of the growing interest in fast
methods, LSC has been considered for a new standard9
on gross alpha- and beta-activity measurement as it
allows the reduction of both sample preparation and
counting times. The adopted methodology entails the
following steps: sample acidification, concentration by
evaporation, addition of a scintillation cocktail, and
alpha/beta discrimination counting. Aspects of
efficiency calibration and alpha/beta discrimination have
been addressed. The new proposed method allows a
considerable reduction of measuring times with respect
to traditional methods, which makes it particularly
suitable for wide drinking water surveys. Additionally,
the increasing use of liquid scintillation counters
requires specific standard procedures.
If a 100 ml water sample is prepared in
approximately 30 minutes and counted for 16 hours, a
minimum detectable activity concentration (MDA) of
0.01 and 0.07 Bq/l for gross alpha- and beta-activity,
respectively, can be achieved. Further reduced counting
times are possible if a lower sensitivity is acceptable.
222Radon measurement
LSC10 was also considered for the measurement of
222Rnin water. The standard method was similar to the
398
one developed by the American Society for Testing and
Materials (ASTM).11 The water sample is introduced
into an LSC vial containing an LSC cocktail non-
miscible with water. Radon is transferred into the
organic phase by shaking, and counted when secular
equilibrium has been established between radon and its
short half-life decay products.
The method proposed in the standard is not
interfered with other radionuclides. A sensitivity of
about 0.5 Bq/l can be obtained with 1-hour counting
time on low-background counting equipment. Portable
instrumentation should ideally comply with the above-
mentioned EU Recommendation,5 although with lower
sensitivities.
Other measurement methods, which use emanometry
or gamma-ray spectrometry and are widely used among
national laboratories, will be considered by the working
group in the near future.
Uranium isotopes measurement
For a new standard concerning uranium isotopes
determination, an ASTM12 standard procedure was
adopted with a few modifications. The procedure is
based on the selective extraction of uranium by a
water-immiscible LSC cocktail that contains bis (2-
ethylhexyl) orthophosphoric acid. In particular, the
chemical composition of the cocktail was investigated
and the extraction procedure optimised in order to
achieve a chemical yield of 95±5%. Extracted uranium
is counted by LSC. Under specific conditions,13 the
alpha-spectrum is software deconvoluted to allow the
determination of the 234U/238U isotopic ratio (these
isotopes are not often in equilibrium in water).
A 1 liter water sample can be prepared in about 1
hour and a minimum detectable activity concentration of
about 0.001 Bq/l can be achieved with a counting time
of 16 hours.
226Ra measurement
A standard on 226Ra-in-water determination is under
study, based on the LSC measurement of 222Rn decay
products. The water sample is acidified and pre-
concentrated by evaporation at moderate temperature.
The initial 222Rn is removed and the sample transferred
into an LSC vial containing an equal volume of water-
immiscible LSC cocktail. After 20 days, the freshly
generated 222Rn that is diffused into the organic phase is
counted.
A 100 ml water sample is prepared in 0.5 hours. This
can be done in parallel with the preparation of the
sample for gross alpha/beta-counting. A 226Ra minimum
detectable activity concentration of about 0.002 Bq/l can
be achieved with a counting time of 16 hours.
 M. FORTE et al.: STANDARDIZED METHODS FOR MEASURING RADIONUCLIDES IN DRINKING WATER

Results and discussion counting procedure were considered. The covariance

Validation of methods
Gross alpha- and beta-activity measurement: The
LSC method was initially validated by ARPA
Lombardia laboratory using internal comparison tests
between LSC and ISO 9696/ISO 9697 results on more
than 30 samples of tap waters and bottled mineral
waters.14,15
The results for gross alpha-activities reported in Fig.
1 show a satisfactory agreement. The same was found
for gross beta activities, although more than 50% of
results were lower than the corresponding minimum
detectable activities.
The LSC method was then applied by ARPA
Lombardia laboratory in an international comparison
organized by the World Health Organisation (WHO).16
The results of this comparison are reported in Table 1.
Finally, the uncertainty budget of the proposed
measurement procedure was thoroughly investigated
according to the relevant ISO standard.17 The
uncertainty components from both sample treatment and
component arising from alpha/beta discrimination
required special investigation.18
222Radon measurement: 222Rn-in-water measurement
results by LSC, emanometry and gamma-ray spectro-
metry were initially compared.19 Standard radon-in-
water sources, supplied by the Italian primary metrology
institute of ENEA,20 were used for method calibration.
Sampling procedures are very important, in particular to
avoid radon escape from water samples. Therefore,
special attention was paid for comparing repeatability
and reproducibility levels for various sampling
techniques.19
During 2003, the working group also promoted a
national comparison on radon-in-water measurements
among Italian laboratories. The results of the newly
developed standard procedure were thus compared with
other traditional procedures. Forty-eight results were
submitted, 21 of which using the LSC method. Some of
the participants used three different techniques (LSC,
gamma-ray spectrometry, emanometry) with results
within ±15% of the reference value.

Fig. 1. LSC and ISO methods: comparison of results. Activity concentrations expressed in Bq/l

Table 1. IRC-CEC intercomparison results

Gross alpha Gross beta

activity concentration, activity concentration,
Bq/l Bq/l
ARPA Lombardia results 0.051 ± 0.010 0.519 ± 0.063
IRC reference values 0.057 ± 0.008 0.520 ± 0.047

399
 M. FORTE et al.: STANDARDIZED METHODS FOR MEASURING RADIONUCLIDES IN DRINKING WATER
Uranium isotopes and 226Ra measurement: Method
validation by internal comparisons is in process at the
ARPA Lombardia laboratory. High-resolution alpha-
spectrometry on electrodeposited samples and mass
spectrometry (ICP-MS) were used as alternative
methods for 238U measurement.
The standard method was also used in the 2003
comparison organized by the International Atomic
Energy Agency (IAEA) on the determination of radium
and uranium radionuclides in water. Results are still
under evaluation by IAEA.
The approach followed by the working group was
considered very satisfactory by all the participants. A
pilot laboratory devoted special effort to study different
methods for the measurement of radionuclides in water.
Already tested methods were proposed and new methods
were validated by comparison with other laboratories
that use different procedures.
Main achievements
The organisation of intercomparisons improved the
quality of all the laboratories. The use of standard
procedures makes it easier to compare the results at the
national level.
Participation in the working group promoted deep
technical discussion and the wide diffusion of accepted
standard procedures.
Technical debate consolidated and enhanced
personal links between experts working in the same
country under the same regulatory requirements.
Conclusions
The UNICEN working group has been set up with
the main task of designing technical standards on
drinking water measurements in order to provide
suitable operative procedures for laboratories
responsible for the verification of normative
requirements imposed by the European Directive
98/83/EC.4 Measurement of radon-in-water parameters
specified in EU Recommendation (2001/928/Euratom)5
is also considered in parallel.
The scarcity of international standards on this subject
required the writing of new documents. Internal
procedures of expert laboratories turned out to be very
useful to this purpose. The most recent technical
advancements were also considered in the light of
accuracy requirements needed for standard technical
procedures.
So far, standard procedures have been produced for
gross alpha/beta-activity and for radon-in-water
measurements. Uranium isotopes and 226Ra standard
measurement methods are still under study. The LSC
technique turned out to be the most adequate one as it is
time saving and yields good sensitivity levels. It was
400
very useful in wide screening situations with a high
number of samples.
Finally, accurate validation work, based on internal
and external comparisons, made it possible to check
both accuracy and reproducibility of the selected
procedures. All the laboratories participating in the
working group benefited from the application of the
method.
As regards future activities, the working group will
consider the following radionuclides: gamma-emitters
(particularly 228Ra, having a high dose coefficient) by
gamma-ray spectrometry on pre-concentrated samples;
long half-life 222Rn decay products (210Pb and 210Po);
thorium isotopes; artificial alpha- or beta-emitters (90Sr
and plutonium isotopes).
*
The authors are grateful to Ms. Monica BROCCO (Istituto
Superiore di Sanità) for the linguistic revision.
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