Ris National Laboratory

Postprint


Radiation Research Department
Year 2007
Paper: www.risoe.dk/rispubl/art/2007_74.pdf

Certified reference material for radionuclides in fish flesh sample IAEA-414 (mixed
fish from the Irish Sea and North Sea)

M.K. Pham, J.A. Sanchez-Cabeza, P.P. Povinec, D. Arnold, M. Benmansour, R.
Bojanowski, F.P. Carvalho, C.K Kim, M. Esposito, J. Gastaud, C.L. Gasc, G.J. Ham, A.G.
Hegde, E. Holm, D. Jaskierowicz, G. Kanisch, M. Llaurado, J. La Rosa, S.-H. Lee, L. Liong
Wee Kwong, G. Le Petit, Y. Maruo, S.P. Nielsen, J.-S. Oh, B. Oregioni, J. Palomares, H.B.L.
Pettersson, P. Rulik, T.P. Ryan, K. Sato, J. Schikowski, B. Skwarzec, P.A. Smedley, S.
Tarjn, N. Vajda, E. Wyse











Required publisher statement
Copyright 2007 Elsevier


Doi: 10.1016/j.apradiso.2006.02.032
1
Certified reference material for radionuclides in fish flesh sample IAEA-414
(mixed fish from the Irish Sea and North Sea)


M.K. Pham
1,@
, J .A. Sanchez-Cabeza
1
, P.P. Povinec
1,#
, D. Arnold
2
, M. Benmansour
3
, R. Bojanowski
4
, F.P. Carvalho.
5
, C.K
Kim
6,*
, M. Esposito
7
, J . Gastaud
1
, C.L. Gasc
8
, G.J . Ham
9
, A.G. Hegde
10
, E. Holm
11
, D. J askierowicz
12
, G. Kanisch
13
, M.
Llaurado
14
, J . La Rosa
1,+
, S.-H. Lee
1,^
, L. Liong Wee Kwong
1
, G. Le Petit
15
, Y. Maruo
16
, S.P. Nielsen
17
, J .-S. Oh
18
, B.
Oregioni
1,$
, J . Palomares
19
, H.B.L. Pettersson
20
, P. Rulik
21
, T.P. Ryan.
22
, K. Sato
23
, J. Schikowski
24
, B. Skwarzec
25
, P.A.
Smedley
26
, S. Tarjn
27
, N. Vajda
28
, E. Wyse
1,&


1
International Atomic Energy Agency (IAEA), Marine Environment Laboratory (MEL), MC 98000 Monaco
2
Physikalisch-Technische Bundesanstalt, Braunschweig, 38116 Germany
3
Centre National de lEnergie, des Sciences et des Techniques Nuclaires (CNESTEN), B.P. 1382, R.P.10001, Rabat, Morocco
4
Institute of Oceanology, Polish Academy of Sciences, PL-81-712 Sopot, Poland
5
Instituto Tecnolgico e Nuclear, Departamento de Proteco Radiolgica e Segurana Nuclear, P- 2685-953 Sacavm, Portugal
6
Dept. of Radiological Environmental Assessment, Korea Inst. of Nuclear Safety, Yo-song, Taejon 305-600, Korea
7
Laboratorio di Ingegneria Nucleare, Universit di Bologna, 40136 Bologna, Italy
8
CIEMAT-DIAE, Radioecologia del Medio Acuatico, 28040 Madrid, Spain
9
National Radiological Protection Board, Chilton, Didcot , Oxon, OX11 0RA, U. K.
10
Environmental Survey Laboratory, Bhabha Atomic Research Center, Tarapur Atomic Power Station, Maharashtra 401 504, India
11
Department of Medical Radiation Physics, Lund University Hospital, 22185 Lund, Sweden
12
Lab. dAnalyses de Surveillance et dExpertise de la Marine, Base Navale de Cherbourg, 50115 Cherbourg, France
13
Federal Research Centre for Fisheries, Institute of Fisheries Ecology, 20539 Hamburg, Germany
14
Lab. de Radiologia Ambiental, Dept. de Quimica Analitica, Facultat de Quimica, Universitat de Barcelona, 08028 Barcelona, Spain
15
Commissariat lEnergie Atomique, DASE /SRCE, 91680 Bruyres-le-Chtel, France
16
Health and Safety Division, JNC Tokai works, Tokai-mura, Naka-gun, Ibaraki 319-1994, Japan
17
Risoe National Laboratory, 4000 Roskilde, Denmark
18
Geosciences Advisory Unit, National Oceanography Centre, Southampton SO14 3ZH, United Kingdom
19
CIEMAT, Instituto de Medio Ambiente, Radioecologia del Medio Acuatico, 28040 Madrid, Spain
20
Dept. of Radiation Physics, Linkoping University Hospital, 58185 Linkoping, Sweden
21
National Radiation Protection Institute, 100 00 Prague 10, Czech Republic
22
Radiological Protection Institute of Ireland, Dublin 14, Ireland
23
Japan Chemical Analysis Center, Inage-Ku, Chiba-Shi, Chiba 263-0002, Japan
24
Physikalische Chemie, Isotopenlabor, Tammannstrabe 6, 37077 Gttingen, Germany
25
Faculty of Chemistry, Chair of Analytical Chemistry, Radiochemical Laboratory, 80-952 Gdansk, Poland
26
CEFAS, Lowestoft Laboratory, Lowestoft, Suffolk NR33 0HT, U. K.
27
National Food Investigation Institute, 1465 Budapest 94, Hungary
28
Institute of Nuclear Techniques, Budapest University of Technology and Economics, 1521 Budapest, Hungary

@
m.pham@iaea.org
# Retired from IAEA-MEL. Present address: Cornenius University, Mlynska dolina F1, Bratislava, Slovakia.


* On leave to Agencys Laboratories, Seibersdorf, A-2444 Seibersdorf, Austria.
+ On leave from IAEA-MEL. Present address: National Institute of Standards and Technology Radioactivity Group Building 245,
Room C111 100 Bureau Drive, Stop 8462 Gaithersburg MD 20899, U.S.A.
^ On leave from IAEA-MEL. Present address: Korea Research Institute of Standards and Science, 1 Doryong-dong, Yuseong-gu,
Taejeon, 305-600, R. O. Korea.
$ Retired from IAEA-MEL.
& On leave from IAEA-MEL. Present address:Frontier GeoSciences Inc., 414 Pontius Ave. N. Seattle, WA 98109, U.S.A.
2

Abstract

A Certified Reference Material (CRM) for radionuclides in fish sample IAEA-414 (mixed fish from
the Irish Sea and North Seas) is described and the results of the certification process are presented.
Nine radionuclides (
40
K,
137
Cs,
232
Th,
234
U,
235
U,
238
U,
238
Pu,
239+240
Pu and
241
Am) were certified for
this material. Information on massic activities with 95% confidence intervals is given for six other
radionuclides (
90
Sr,
210
Pb(
210
Po),
226
Ra,
239
Pu,
240
Pu
241
Pu). Less frequently reported radionuclides
(
99
Tc,
129
I,
228
Th,
230
Th and
237
Np) and information on some activity and mass ratios are also included,
The CRM can be used for quality assurance/quality control of the analysis of radionuclides in fish
sample, for the development and validation of analytical methods and for training purposes. The
material is available from IAEA, Vienna, in 100g units.

3

Introduction

Accurate and precise determination of radionuclide concentrations in marine samples is important for
marine radioactivity assessments and for the use of radionuclides in the study of oceanographic
processes. To address the problem of data quality, the IAEA Marine Environment Laboratory (IAEA-
MEL) in Monaco has conducted intercomparison exercises on radionuclides in marine samples for
many years as part of its contribution to the IAEAs programme of Analytical Quality Control Service
(AQCS) [1-2]. An important part of this activity was the production of Reference Materials (RMs),
which were usually products of worldwide intercomparison exercises. Regional intercomparison
exercises generally resulted in Reference Materials with only information values on radionuclide
concentrations.

RMs are samples with well established properties used for the assessment of analytical methods.
Certified Reference Materials (CRMs) or Standard Reference Materials (issued by the National
Institute of Standard and Technology NIST) [3] have property values certified by technically
validated procedures (at least two independent analytical methods used) traceable to SI units [4-5].
RMs and CRMs are valuable for method development and validation: they can indicate the need to
improve or change existing methods and/or the need of further training. In fact, reference methods
should only be accepted on the basis of interlaboratory tests performed on selected CRMs.

The IAEAs AQCS programme for radionuclides in the marine environment has recently focused on
the production of CRMs, to improve the accuracy and precision of analyses carried out by the
laboratories and thus the quality of data, and to provide traceability to SI standards. CRMs should be
available for all important marine matrices, such as sediment, biota, sea water, suspended matter,
etc
4

This work was performed on a sample with enhanced radionuclide levels due to discharges from the
Sellafield nuclear reprocessing plant. Participating laboratories were requested to determine as many
anthropogenic radionuclides as possible by gamma spectrometry and other radionuclides requiring
radiochemical separation (notably transuranics) by alpha spectrometry, beta counting and/or mass
spectrometry. The certification process was completed and the material was issued as a CRM for
radionuclides in fish flesh.

5

Methods

Description of the material

About 350 kg of mixed fish species were collected in the eastern Irish Sea by the Center for
Environment, Fisheries and Aquaculture Science (CEFAS), Lowestoft, U.K., in 1996. The skin was
removed, the fish filleted and freeze-dried and subsequently sent to IAEA-MEL for processing. The
sample, which was reduced by freeze-drying to about 69 kg, was then ground to powder, sieved
through a 0.5 mm mesh and homogenized by mixing in a nitrogen atmosphere. The sample was
freeze-dried once more, ground and sieved at 250 m to obtain a final amount of 10 kg. As the
quantity of material obtained was small and the measured activities of some anthropogenic
radionuclides were relatively high, the sample was mixed with 100 kg of North Sea fish powder
(fraction below 250 m) to get the required quantity. To ensure homogenization of the final sample,
both samples (fractions <250 m) were mixed by jet pulverizing in a nitrogen atmosphere. The
samples were then packed into brown glass bottles under nitrogen gas, sealed with polyethylene caps
and labeled with the code IAEA-414. The sealed glass bottles containing 100 g of fish powder were
sterilized according to ISO standards [4] at 10 kGy in an irradiation facility. The average moisture
content of the lyophilized sample after bottling, determined by drying several aliquots in an oven at
80 C to constant weight (1-2 days), was found to be approximately 3%.

Sample homogeneity was checked by measuring the activity of
40
K,
137
Cs,
210
Po,
235
U,
238
U,
238
Pu,
239+240
Pu and
241
Am of 16-30 bottles randomly chosen. Gamma spectrometry measurements were
performed on 30 to 100 g aliquots.
210
Po,
235
U,
238
U,
238
Pu,
239+240
Pu and
241
Am were determined by
alpha spectrometry on 0.1 to 20 g aliquots. Homogeneity of these results was checked using one-way
analysis of variance. The coefficient of variation was below 10% for radionuclides measured by
6
gamma and alpha spectrometry. The "between samples" variances showed no significant differences
from the "within sample" variances for all radionuclides tested. Thus the material could be considered
sufficiently homogeneous for the tested radionuclides at the range of weights used.

Certification process

The sample was used in the worldwide intercomparison exercise IAEA-414 Radionuclides in mixed
fish from Irish Sea and North Sea. The results of this exercise, including recommended and
information values, were reported elsewhere [6]. Laboratory means were calculated from individual
results as arithmetic means with corresponding uncertainties when more than two results were
reported. In the case that only two results reported, and in order to take into account possible large
differences in uncertainties, laboratory means were calculated as weighted means with weighted
uncertainties, as no further statistical treatment possible in this case. All values were rounded off to
the most significant digit. ISO Guide 35 [4] recommends that a result suspected to be an outlier
should be removed. The less than values were segregated from the results, the remaining values
were checked for the presence of outliers using a box and whisker plot test and not taken into
consideration when calculating medians and confidence intervals. Calculations were based on the
assumption that data followed a non-parametric distribution to which distribution-free statistics are
applicable. Confidence intervals were determined from a non-parametric sample population and
expressed as a two-sided interval representing 95% confidence limits.

Calculation of certified values was based on the ISO approach of certification through a series of
measurements [4]. For data sets comprising 5 or more accepted laboratory means, median values and
confidence intervals were calculated for true massic activities and were considered as certified values
when (i) these data were produced by at least 3 different laboratories, as one laboratory can provide
different data sets to analyze the same radionuclide, (ii) the relative uncertainty of the median did not
7
exceed 5% for activities higher than 100 Bq kg
-1
, 10% for activities from 1 to 100 Bq kg
-1
and
20% for activities lower than 1 Bq kg
-1
. An activity value was considered to be an information value
when these data sets were produced by at least 2 different laboratories, independently of the
uncertainty reported.

More strict criteria were used in the certification process than those described in the ISO Guide 35 [4].
Several expert laboratories provided additional high accuracy data obtained by radiometric and mass
spectrometric techniques. Because these data were received before the intercomparison exercise was
finalised, they were also included in the intercomparison report [6]. Only data included in the 95%
confidence interval of the distribution for each radionuclide were included in the certification
analysis. The same statistical procedures were applied to the smaller datasets, thus providing slightly
different and more precise estimations of the true activities. Any systematic bias among the data sets
that could be due to sample inhomogeneity or differences in analytical methods was carefully
examined. Results of the new data evaluation were considered to be the certified massic activities.

8

Results and discussion

Radionuclides with certified activities

IAEA-414 was certified for 9 radionuclides. The certified massic activities (medians) for
40
K,
137
Cs,
232
Th,
234
U,
235
U,
238
U,
238
Pu,
239+240
Pu and
241
Am and the corresponding 95% confidence intervals are
given in Table 1. All results are expressed in Bq kg
-1
dry weight (dw). All data sets showed good
homogeneity, within 2 standard deviations of the mean.

40
K: Data reported from 19 laboratories were used in the certification process. Non-destructive
gamma spectrometry was used for the direct analysis of
40
K. The median, given as the
certified value is 481 Bq kg
-1
dw (the 95% confidence interval is (470-486) Bq kg
-1
dw).
137
Cs: Data reported from 16 laboratories were used in the certification process (Fig. 1). Mostly non-
destructive gamma spectrometry was used. A few laboratories performed either (i) co-
precipitation with MnO
2
and hexacyanoferrate or (ii) quantitative scavenging with AMP
followed by gamma spectrometry. This latter method helps to reduce the detection limit by
using the well-type HPGe detector with higher efficiency. The certified value (median) is 5.18
Bq kg
-1
dw (the 95% confidence interval is (5.12-5.22) Bq kg
-1
dw).

Other than the conventional non-destructive gamma spectrometry, a counting technique frequently
used to determine natural radionuclides was semiconductor alpha spectrometry (SAS), after Th and U
separation from the sample using either ion exchange or TRU and UTEVA resins and electro-
deposition. Some laboratories used mass spectrometry techniques (Inductively Coupled Plasma Mass
9
Spectrometry (ICPMS) and Accelerator Mass Spectrometry (AMS)) or both mass spectrometry and
SAS for determination of uranium isotopes.

232
Th: Data reported from 6 laboratories were used in the certification process. The certified value
(median) is 0.028 Bq kg
-1
dw (the 95% confidence interval is (0.025-0.031) Bq kg
-1
dw).
234
U: Data reported from 8 laboratories were used in the certification process. The certified value
(median) is 1.22 Bq kg
-1
dw (the 95% confidence interval is (1.15-1.26) Bq kg
-1
dw).
235
U: Data reported from 9 laboratories were used in the certification process. The certified value
(median) is 0.050 Bq kg
-1
dw (the 95% confidence interval is (0.045-0.055) Bq kg
-1
dw).
238
U: Data reported from 9 laboratories were used in the certification process (Fig. 2). The data
showed very good homogeneity, within two standard deviations of the distribution mean, using
different analytical techniques such as SAS, ICPMS or AMS. The median given as the certified
value is 1.11 Bq kg
-1
dw (the 95% confidence interval is (1.07-1.15) Bq kg
-1
dw).

The counting technique most widely used to determine transuranics was SAS, after separation using
different methods: (1) ion exchange and electrodeposition, (2) ion exchange, liquid-liquid extraction
(TIOA, DDCP) and electrodeposition, (3) Ca oxalate precipitation, TRU resins, SCN-anion exchange,
electrodeposition and (4) double columns TEVA+TRU resins and electrodeposition. In a few cases,
mass spectrometry techniques such as ICPMS, TIMS and AMS were used for
239
Pu,
240
Pu and
241
Pu
determination. In this case, the final step of sample preparation was quite different. Instead of
electrodeposition, the Pu sample was dissolved in 1M HNO
3
(for ICPMS and TIMS) or mixed with a
Fe solution and evaporated.

238
Pu: Data reported from 11 laboratories were used in the certification process. No discrepancies
were noticed in the results obtained using different separation methods. The certified value
(median) is 0.0230 Bq kg
-1
dw (the 95% confidence interval is (0.0221-0.0250) Bq kg
-1
dw).
10
239+240
Pu: Data reported from 14 laboratories were used in the certification process (Fig. 3). Both
alpha spectrometry and mass spectrometry techniques were used for
239+240
Pu determination.
Most analyses were performed using conventional alpha spectrometry, and some data were
combinations from ICPMS, TIMS and AMS as analyses. It was noticed that data obtained by
mass spectrometry showed, generally speaking, slightly higher values. Meanwhile no
discrepancies were noticed in the results obtained using different chemical separation methods
and using SAS. Further investigation is under way to understand the differences between SAS
and mass spectrometry analyses. The certified value (median) is 0.120 Bq kg
-1
dw (the 95%
confidence interval is (0.116-0.123) Bq kg
-1
dw).
241
Am: Data reported from 9 laboratories were used in the certification process. Most analyses were
done by alpha spectrometry. The precision of a few data obtained by gamma spectrometry was
much lower. However, as these results were not outliers, they were included in the
certification process. The median certified value (median) is 0.197 Bq kg
-1
dw (the 95%
confidence interval is (0.193-0.204) Bq kg
-1
dw).

Radionuclides with information activities
Information on the massic activities with the corresponding 95% confidence interval is given for 6
radionuclides (
90
Sr,
210
Pb(
210
Po),
226
Ra,
239
Pu,
240
Pu and
241
Pu) in Table 2. All results are expressed in
Bq kg
-1
dry weight (dw).

90
Sr: Data reported from 6 laboratories were used in the certification process. Several methods were
used to extract Sr from the fish sample although the most frequently used was precipitation of
oxalate or hydroxide, separation by concentrated or fuming nitric acid, scavenging of Ra and
Fe, two weeks in-growth and beta counting of
90
Y (as Y
2
O
3
). Although data were homogenous,
the uncertainties were high due to the difficulty of dealing with Sr separation in the presence of
11
highly insoluble SrSO
4
in the fish sample. The median given as the information value is 0.28
Bq kg
-1
dw (the 95% confidence interval is (0.10-0.54) Bq kg
-1
dw).
210
Pb(
210
Po): Data reported from 11 laboratories were used in the certification process. Taking into
account the time elapsed between sample collection and analysis, it seems reasonable to assume
secular equilibrium between
210
Pb and
210
Po. Mainly gamma spectrometry and alpha
spectrometry (
210
Po in-growth) were used for
210
Pb determination. Although the data showed
good homogeneity, uncertainties were high due to the difficulty to properly calibrate low-
energy gamma emitters at low concentrations. The information value (median) is 2.1 Bq kg
-1

dw (the 95% confidence interval is (1.8-2.5) Bq kg
-1
dw).
226
Ra: Data reported from 9 laboratories were used in the certification process. Most laboratories used
gamma spectrometry for
226
Ra determination. A few laboratories used radiochemical methods
prior to alpha-spectrometry. Although the data showed good homogeneity, uncertainties could
be caused by wrong background subtraction and possible interferences in the 186 keV line with
235
U when using gamma-spectrometry. The information value (median) is 1.4 Bq kg
-1
dw (the
95% confidence interval is (0.6-1.6) Bq kg
-1
dw).
239
Pu: Data reported from 10 laboratories were used in the certification process. Only mass
spectrometry (ICPMS, AMS) were used for
239
Pu determination. Although the data showed
good homogeneity, the overall uncertainty was quite high. The median given only as the
information value is 0.066 Bq kg
-1
dw (the 95% confidence interval is (0.055-0.073) Bq kg
-1

dw).
240
Pu: Data reported from 10 laboratories were used in the certification process. Only mass
spectrometry techniques were used for
240
Pu determination due the interference of
239
Pu in the
SAS alpha-spectra. No discrepancies were noticed in the reported results obtained using
different techniques. The median given only as the information value is 0.047 Bq kg
-1
dw (the
95% confidence interval is (0.046-0.051) Bq kg
-1
dw).

12
241
Pu: Eleven laboratory means obtained by ICP-MS and liquid scintillation were evaluated. No
differences were noticed in results obtained using different techniques. The median given as the
information value is 2.0 Bq kg
-1
dw (the 95% confidence interval is (1.8-2.3) Bq kg
-1
dw).

Less frequently reported radionuclides
99
Tc: The four results reported gave an average massic activity of (6.70.3) Bq kg
-1
dw.
129
I: Three laboratories reported mean values giving an average massic activity of 9.70.1 mBq kg
-1

dw.
228
Th: Four laboratories reported mean values giving an average massic activity (0.1910.002) Bq kg
-
1
dw. They were determined using conventional alpha spectrometry with prior chemical
separation as for
230
Th and
232
Th.
230
Th: Four laboratories reported mean values giving an average massic activity of 0.0450.001 Bq
kg
-1
dw.
237
Np: Two results were reported. One was the weighted mean of two values (0.320.06) Bq kg
-1
dw
determined by SAS. The other one was an average massic activity of 3 values (1.50.3) Bq kg
-
1
dw determined by gamma spectrometry with prior chemical separation.

Radionuclide ratios
The radionuclide ratios for Sr, Cs, Pu and Am isotopes are given in Table 3. They were expressed in
activity ratios or mass ratio depending on the techniques used. The
238
Pu/
239+240
Pu activity ratio
(0.1910.008) is higher than the expected global fallout ratio from nuclear weapons tests in these
latitudes (0.025-0.04) [9] and close to the ratio found in Irish Sea water (0.240.03) [8], confirming
that the enhanced Pu concentration in the sample is due to discharges from the Sellafield reprocessing
plant. The
241
Am/
239+240
Pu activity ratio (1.670.08) is higher than the expected global fallout ratio
from nuclear weapons tests (0.370.10) [10] and slightly higher than the ratio from Irish Sea water
(1.160.26) [8] and may indicate an enhanced uptake of
241
Am by fish.

13

Conclusions

A mixed fish sample from the Irish Sea and North Sea collected in 1996 has been certified for
radionuclides according to ISO certification criteria and has been issued as the Certified Reference
Material IAEA-414.

IAEA-414 has been certified for 9 radionuclides (
40
K,
137
Cs,
232
Th,
234
U,
235
U,
238
U,
238
Pu,
239+240
Pu
and
241
Am). Information values have also been obtained for 6 radionuclides (
90
Sr,
210
Pb(
210
Po),
226
Ra,
239
Pu,
240
Pu and
241
Pu). IAEA-414 is intended to be used for quality assurance/quality control of the
analysis of radionuclides in the fish sample for the marine environment carried out by radiometric and
mass spectrometry techniques (ICPMS, TIMS, AMS), for the development and validation of
analytical methods, for the preparation of reference methods and for training purposes. The CRM is
available from the IAEA in 100g units and can be ordered through our website:
http:///www.iaea.org/programmes/naal/

Acknowledgment

The authors are indebted to their numerous colleagues who took part in the analytical work. Special
acknowledge is given to the Center for Environment, Fisheries and Aquaculture Science (CEFAS),
Lowestoft, United Kingdom (U.K.) for providing the fish sample. The IAEA is grateful for the
support provided to its Marine Environment Laboratory by the Government of the Principality of
Monaco.


14
References

[1]. J .A. Sanchez-Cabeza, M.K. Pham and P. Povinec, Quality of marine radioanalytical data,
Accreditation and Quality Assurance (in press).
[2]. P.P. Povinec and M.K. Pham, IAEA Reference Materials for quality assurance of marine
radioactivity measurements. J. Radioanalytical and Nuclear Chemistry, Vol. 248, No.1, pp.
211-216, (2001).
[3]. K. Inn et al., The NIST Natural Matrix Radionuclides Standard Reference Material Program for
Ocean Studies, in: Marine Pollution, Book of Extended Synopses, pp. 53, (1998).
[4]. ISO, Certification of Reference Materials General and Statistical Principles, Guide 35, ISO,
Geneva, 60 p. (2004).
[5]. ISO, Quality System Guidelines for the Production of Reference Materials, Guide 34, ISO/IEC,
Geneva, (1996).
[6]. M.K. Pham, J . La Rosa, S.-H. Lee and P.P. Povinec, Radionuclides in Mixed Fish from Irish Sea
and North Sea. Report on the world-wide intercomparison IAEA-414, IAEA/AL/145,
IAEA/MEL/73. 81 p. (2004).
[7]. UNSCEAR, 1993. Source and Effects of Ionising Radiation. United Nations, New York.
[8]. P.P. Povinec et al., Certified reference material for radionuclides in seawater IAEA-381 (Irish Sea
Water). J. Radioanalytical and Nuclear Chemistry, Vol. 251, No. 3, pp. 369-374, (2002).
[9]. D.H. Oughton, L. Skipperud, B. Salbu, L.K. Fifield, R.C. Cresswell and J .P. Day. Determination
of
240
Pu/
239
Pu isotope ratios in Kara Sea and Novaya Zemlya sediments using accelerator mass
spectrometry. In: Marine Pollution, IAEA-TECDOC-1094, pp. 123-128 (1999).
[10]. T.P. Ryan, P.I. Mitchell, J .A. Sanchez-Cabeza, V. Smith, J . Vives I Battle. Distribution of
radioactive fallout throughout Ireland. In: Proc Int Tyndall School and National Environmental
Week, Carlow (Ireland). 11-19 September 1993. Science, Green Issues and the Environment:
Ireland and the Global Crisis 1995: 276-282.
15
Table 1. Certified massic activities in IAEA-414 (mixed fish from the Irish Sea and North Seas)

Radionuclide
Mean Std. Dev.
(Bq kg
-1
)
Median
(Bq kg
-1
)
95% confidence
interval (Bq kg
-1
)
N*

40
K 48012 481 470-486 19
137
Cs 5.170.09 5.18 5.12-5.22 16
232
Th 0.0280.002 0.028 0.025-0.031 6
234
U 1.200.05 1.22 1.15-1.26 8
235
U 0.0500.004 0.050 0.045-0.055 9
238
U 1.110.04 1.11 1.07-1.15 9
238
Pu 0.02300.0013 0.0230 0.0221-0.0250 11
239+240
Pu 0.1200.004 0.120 0.116-0.123 14
241
Am
#
0.2000.009 0.197 0.193-0.204 9
Reference date for decay correction: 1 J anuary 1997.
* Number of accepted laboratory means which were used to calculate the certified massic activities and the corresponding confidence intervals.
#The values should be corrected for in-growth from
241
Pu.


Table 2. Information massic activities in IAEA-414 (mixed fish from the Irish Sea and North Sea)

Radionuclide
Mean Std. Dev.
(Bq kg
-1
)
Median
(Bq kg
-1
)
95% confidence
interval (Bq kg
-1
)
N*

90
Sr 0.300.19 0.28 0.10-0.54 6
210
Pb(
210
Po)

2.10.4 2.1 1.8-2.5 11
226
Ra 1.30.4 1.4 0.6-1.6 9
239
Pu 0.0650.008 0.066 0.055-0.073 10
240
Pu 0.0470.003 0.047 0.046-0.051 10
241
Pu 2.10.3 2.0 1.8-2.3 11
Reference date for decay correction: 1 J anuary 1997.
* Number of accepted laboratory means which were used to calculate the certified massic activities and the corresponding confidence intervals.


Table 3. Radionuclide activity ratios
137
Cs/
90
Sr
137
Cs/
239+240
Pu
238
Pu/
239+240
Pu
241
Pu/
239+240
Pu
241
Am*/
239+240
Pu
240
Pu/
239
Pu**
1711 43.10.8 0.1910.008 172 1.670.08 0.70.1

* The values should be corrected for in-growth from
241
Pu.
** Mass ratio


16

FIGURES

Fig. 1. Data used in the certification of
137
Cs (the median (full line) and corresponding 95%
confidence intervals (dashed lines) are also shown).

Fig. 2. Data used in the certification of
238
U (the median (full line) and corresponding 95% confidence
intervals (dashed lines) are also shown).

Fig. 3. Data used in the certification of
239+240
Pu (the median (full line) and corresponding 95%
confidence intervals (dashed lines) are also shown).

17






Figure 1 (Pham et al.)


137
Cs
Result number
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
B
q

k
g
-
1
4.50
4.75
5.00
5.25
5.50
5.75
6.00
18





Figure 2 (Pham et al)

238
U
Result number
1 2 3 4 5 6 7 8 9
B
q

k
g
-
1
0.6
0.8
1.0
1.2
1.4
1.6
19



Figure 3 (Pham et al)


239+240
P u
Result number
1 2 3 4 5 6 7 8 9 10 11 12 13 14
B
q

k
g
-
1
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.18