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TitleSpeciation of Long-Lived Radionuclides in the Environment
LanguageEnglish
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Table of Contents
                            paper-2-JER-Dynamic adsorption2008.pdf
	Evaluation of the readsorption of plutonium and americium in dynamic fractionations of environmental solid samples
		Introduction
		Experimental
			Instrumentation
			Extraction column
			Modified SM&T sequential extraction scheme
			Procedure for readsorption study
			Batch extraction
			General procedure for dynamic extraction
			Soil samples
			Dissolution of residues and determination of total concentrations of radionuclides and metals
		Results and discussion
			Dynamic sequential extractions
			Choice of extractant for the exchangeable fraction
			Comparison of the degree of readsorption for dynamic and batch systems
			Distribution of Pu and Am and method validation
		Conclusion
		Acknowledgements
		References
paper-3-129I-speciation-review-ACA2008.pdf
	A review on speciation of iodine-129 in the environmental and biological samples
		Introduction
		Iodine in the nature and its speciation
			Speciation of iodine in water
			Speciation of iodine in biological and environmental samples
			Speciation of iodine in atmosphere
			Speciation of iodine in soil and sediment
		Sources, inventory, and concentration level of 129I in the environment
		Measurement of 129I
			Gamma and X-ray spectrometry
			Liquid scintillation counting (LSC)
			Neutron activation analysis
			Accelerator mass spectrometry (AMS)
			Inductively coupled plasma mass spectrometry (ICP-MS)
		Speciation analysis of 129I in environmental and biological samples and its application
			Speciation of 129I in water
			Speciation of 129I in atmosphere
			129I speciation in soil and sediment
			129I speciation in biological samples
		Bioavailability and radiation toxicity of 129I
		Summary and perspectives
		Acknowledgements
		References
Paper-4-ACA-review-article-2008.pdf
	Critical comparison of radiometric and mass spectrometric methods for the determination of radionuclides in environmental, biological and nuclear waste samples
		Introduction
		Radiometric methods
			Alpha spectrometry
			Gamma spectrometry
			Beta counting
		Mass spectrometry
			Inductively coupled plasma mass spectrometry
			Accelerator mass spectrometry
			Thermal ionization mass spectrometry
			Resonance ionization mass spectrometry
			Secondary ion mass spectrometry
			Glow discharge mass spectrometry
		Comparison of radiometric and MS methods for the determination of radionuclides
			Tritium
			Carbon-14
			Chlorine-36
			Calcium-41
			Nickel-59, 63
			Stronium-89, 90
			Technitium-99
			Iodine-129
			Cesium-135, 137
			Lead-210
			Radium-226, 228
			Isotopes of thorium and uranium
			Neptunium-237
			Plutonium isotopes
			Amerium-241
		Application of on-line methods (flow injection/sequential injection) for separation of radionuclides
		Conclusion
		Acknowledgements
		References
Paper-5-Handbook of Iodine-CH015-iodine speciation-2009.pdf
	Iodine Speciation in Foodstuffs, Tissues, and Environmental Samples: Iodine Species and Analytical Method
		Abstract
		Abbreviations
		Introduction
		Speciation of Iodine in Water
			Distribution of Iodine Species
			Speciation Analysis of Inorganic Iodine
			Speciation Analysis of Volatile Organic Iodine
			Speciation Analysis of Iodine in Freshwater
		Chemical Speciation of Iodine in Air
			Iodine Species
			Speciation Analysis of Iodine
			Speciation Analysis of Volatile Iodine
		Chemical Speciation of Iodine in Tissues and Biological Samples
			Species of Iodine
			Speciation Analysis of Iodine in Tissues
			Speciation Analysis of Iodine in Hydrolyzed Solution of Tissues, Urine and Serum
		Chemical Speciation of Iodine in Foodstuffs and Environmental Samples
			Speciation Analysis of Iodine in Milk
			Speciation Analysis of Iodine in Fish
			Speciation Analysis of Iodine in Seaweeds
		Bioavailability and Toxicity of Iodine Species
			Bioavailability of Iodine Species
			Toxicity of Excessive Intake of Iodine
			Toxicity of Iodine Species
		Summary Points
		References
	Untitled
                        
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Speciation of Long-Lived Radionuclides in the Environment

Hou, Xiaolin

Publication date:
2008

Document Version
Publisher's PDF, also known as Version of record

Link back to DTU Orbit

Citation (APA):
Hou, X. (2008). Speciation of Long-Lived Radionuclides in the Environment. Roskilde: Danmarks Tekniske
Universitet, Risø Nationallaboratoriet for Bæredygtig Energi. Denmark. Forskningscenter Risoe. Risoe-R, No.
1677(EN)

Page 2

Chemical Speciation of Long-Lived
Radionuclides in the Environment

Xiaolin Hou

Risø-R-1677(EN)

Risø National Laboratory for Sustainable Energy
Technical University of Denmark

Roskilde, Denmark
November 2008

Page 73

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X. Hou et al. / Analytica Chimica

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ig. 2. Liquid discharges of 129I from spent nuclear fuel reprocessing plants at La
ague (France), Marcoule (France) and Sellafield (UK) (literature refers to the text).

29I has been released to the atmosphere from the three reprocess-
ng plants with a relative constant rate of each (2–10 kg y−1). The

arine discharges of 129I from La Hague and Sellafield is smaller
nd relatively constant before 1990 (<50 kg y−1), later on the dis-
harge of 129I increased significantly to about 250 kg y−1 for La
ague and 80 kg y−1 for Sellafield. As a consequence, the 129I con-
entration in the Irish Sea, English Channel, North Sea, and Nordic
eas has significantly increased and the 129I/127I ratio in these sea-
ater has elevated to values of 10−8 to 10−5 [6,7,11–15,23,103–108].

ven high level of 129I concentration with a ratio of 129I/127I at
0−6 to 10−4 has been measured in the terrestrial samples collected
ear the reprocessing plants at La Hague, Marcoule and Sellafield
77,105,109]. These high ratios are attributed to local deposition of
tmospheric releases of 129I from the reprocessing plants. 129I has
lso been released from other reprocessing plants mainly to atmo-
phere, in which Hanford reprocessing plant (USA) released about
60 kg 129I during its operation (1944–1972) [110] and about 14 kg
uring its resumed operation (1983–1988) [82]; reprocessing plant
t Tokai, Japan released about 1.0 kg 129I since its operation from
997 until 2005 [111,112]; about 1.1 kg of 129I was released from the

arlsruhe reprocessing plant (WAK, Germany) during its operation

1971–1987) [113], and unknown amount of 129I from reprocess-
ng plants in Russia, China and India. An elevated 129I levels with
29I/127I ratio of 10−6 to 10−4 have been also reported in samples col-

ig. 3. Atmospheric releases of 129I from spent nuclear fuel reprocessing plants at
a Hague (France), Marcoule (France) and Sellafield (UK).

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Acta 632 (2009) 181–196 185

ected in the regions near the reprocessing plants at WAK, Germany,
anford, USA, Tokai, Japan, and India [98,13–116].

Table 2 summarizes the sources, inventory and environmental
evel of 129I. It is clear that presently the main source of 129I is the
eprocessing plants at La Hague and Sellafield. However, the major
art of 129I produced in reactors around the world, mainly power
eactor (>90%), is still stored and pending for future reprocessing.
t present, the different levels of 129I/127I in the environment are
nvisaged as 10−12 for the pre-nuclear era, 10−9 in slightly contam-
nated regions and 10−9 to 10−6 in regions affected by the releases
rom the reprocessing plants. The highest ratio of 129I/127I at 10−6

o 10−3 was found in regions locating at the vicinity (<50 km) of the
eprocessing plants.

. Measurement of 129I

129I decays by emitting �-particle with a maximum energy
f 154.4 keV and �-ray of 39.6 keV as well as X-rays (29–30 keV)
Table 1). It can therefore be measured by �–X-spectrometry
nd �-counting using liquid scintillation counters (LSC). Neutron
ctivation analysis (NAA) is another radiometric method for the
etermination of 129I. The method is based on neutron activation
f 129I to 130I, a short-lived radionuclide, emitting high-energy �-
ays (536 keV (99%), 668.5 keV (96%), and 739.5 keV (82%)), which is
asily and efficiently measured by �-spectrometry. Mass spectrom-
try, such as accelerator mass spectrometry (AMS) and inductively
oupled plasma mass spectrometry (ICP-MS) has also been used for
he determination of 129I. A summary of the most common used

ethods is presented below.

.1. Gamma and X-ray spectrometry

Gamma and X-ray spectrometry have been used to measure 129I
n thyroid, urine, seaweed, and nuclear waste by using HpGe or
lenary Si detector [104–106,117,118]. This is based on the count-

ng the 39.6 keV �-ray or 29.46 + 29.48 keV (58.1%) X-rays. Due
o the low counting efficiency of gamma detector (< 2%), low �-
ay abundance (7.5%), and high background, a detection limit of
0–200 mBq was obtained [104,117,118] depending on the level of

nterfering radionuclides. In addition, due to the low energy of X–�
ays (29–40 keV) and normally big sample used (50–500 g), elab-
rative self-absorption correction has to be carried out in order
o obtain accurate results. A chemical separation of iodine from
he matrix and interfering radionuclides can improve the detec-
ion limit to around 20 mBq when using gamma spectrometry. In
ddition, due to small size of the separated sample (<20 mg), the
elf-absorption correction can be neglected.

.2. Liquid scintillation counting (LSC)

Due to high beta energy of 129I (154 keV), a better counting effi-
iency of LSC for 129I (60–95%) compared with X–�-spectrometry
<5%) can be obtained depending on the quench level. In this

ethod, iodine has to be separated from the sample matrix as well
s other radionuclides before counting. A detection limit of 10 mBq
as been reported [117].

.3. Neutron activation analysis
Neutron activation analysis was firstly proposed and applied in
962 [79,119] for the determination of 129I, which based on the
ollowing nuclear reaction:

29I
(n,�), �=30b, I=27.6b−−−−−−−−−−−−−→130I�

−, 12.3h−−−−−→130Xe

Page 74

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186 X. Hou et al. / Analytica Chimica Acta 632 (2009) 181–196

Table 2
Sources, inventory/releases and environmental level of 129I.

Source Inventory/release (kg)a 129I/127I ratio in the environment Referenceb

Nature 250 ∼1 × 10−12 [81–83]
Nuclear weapons testing 57 1 × 10−11 to 1 × 10−9 [26,35,83–89]
Chernobyl accident 1.3–6 10−8 to 10−6 (in contaminated area) [22,36,89,94–96,127]
Marine discharge from European NFRP by 2007 5200 10−8 to 10−6 (North Sea and Nordic Sea water) [6,7,11,13–15,23,103,104,106–108]

Atmospheric release from European NFRP by 2007 440 10−8 to 10−6 (in rain, lake and river water in
west Europe)

[16,125,126,128]

10−6 to 10−3 (in soil, grass near NFRP) [77,105,109,113]

Atmospheric release from Hanford NFRP 275 10−6 to 10−3 (in air near NFRP) [98,115]

roces
s efers t

ing pla

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a Marine discharge refers to the sum discharges from La Hague and Sellafield rep
um of those from La Hague, Sellafield, Marcoule and WAK. The source of the data r

b The references for the environmental level of 129I; NFRP: nuclear fuel reprocess

y measurement of activation product, 130I (12.3 h), decaying by
mitting beta particles and gamma rays (Table 1), 129I is deter-
ined. Using NAA, 129I can be determined with a better sensitivity

ompared with the direct measurement due to the high specific
adioactivity of 130I and suitable gamma energies (418 keV (34%),
36.1 keV (99%), 668.5 keV (96%), and 739.5 keV (82%)). However,

nterfering nuclear reactions from some nuclides other than iodine
sotopes may occur during production of 130I in the samples. These
uclides include 235U, 128Te, and 133Cs. Because of the extremely

ow concentration of 129I in environmental samples (10−17 to
0−11 g g−1), these interfering nuclides have to be removed from
he sample before irradiation to avoid nuclear interference that
ill generate spurious results. The radioactivity produced from the

ctivation products of the sample matrix elements, such as 24Na
nd 82Br, is more than 10 orders of magnitude higher than that of
30 130
I, which hinders the direct measurement of I after irradia-
ion. Bromine in particular, produces �-rays of 82Br that interferes
ith the measurement of 130I, which necessities a post-irradiation

hemical purification to provide a necessary decontamination with
espect to this nuclide. Besides 129I, stable iodine (127I) can be simul-

a
i
a
t
a

Fig. 4. Diagram of analytical procedure for the de
sing plants; the atmospheric release from European reprocessing plant refers to a
o the literatures cited in the text.
nt.

aneously determined by fast neutron reaction 127I(n, 2n)126I. A
ypical analytical procedure for the determination of 129I by radio-
hemical NAA [120] is shown in Fig. 4.

For solid sample, such as soil, sediment, vegetations and tissues,
lkali fusion/ashing method can be used for decomposition of sam-
le, in which the sample is first mixed with alkali solution, and then
shed or fussed at 600 ◦C. Iodine is then leached from the decom-
osed sample using water. The experimental results have showed
hat the recovery of iodine in ashing or fusion procedure is higher
han 80% [121]. A combustion method has also widely been used
or the separation of iodine from solid samples [121,122]. In this

ethod, sample is combusted at higher temperature (>800 ◦C), the
eleased iodine, mainly as I2, is trapped with alkali solution (KOH)
r active charcoal. Iodine in the leachate or trapping solution is
xtracted with CCl4 (or CHCl3) after acidified and oxidized to I2,

nd then back extracted with H2SO3. After conversion of separated
odine to MgI2, it is applied for neutron irradiation. Fig. 5 shows

commercial combustion facility, which can be used for separa-
ion of iodine from solid sample. For water sample including milk
nd urine, iodine can be separated by anion exchange method. In

termination of 129I by radiochemical NAA.

Page 146

J. JERNSTRÖM et al.: ON-LINE SEPARATION OF Pu(III) AND Am(III)

102

In order to quantitatively separate trivalent
plutonium and americium in CS5A column it was
therefore, necessary to use two different eluents. ~99%
of Pu eluted from the column between 26 and 32
minutes by using dipicolinic acid eluent; ~98% of Am
eluted between 2 and 6 minutes with oxalic acid eluent
(Fig. 5). The elution of plutonium was followed by
rinsing the column for 10 minutes with dipicolinic acid
solution, after which the elution of americium followed.
The eluted plutonium and americium fractions were
measured with alpha-spectrometry, and were found to be
radiochemically and chemically pure.

Conclusions

A previously developed on-line method for
separation of americium from environmental samples
has been modified to include separation of plutonium.
The novel procedure is based on reducing plutonium to
trivalent oxidation state, when it follows the behavior of
americium throughout the separation processes. The
elution of Pu and Am from the final separation column
was done with two different eluents, and
radiochemically pure quantitative separation of both
elements was achieved. Further studies are needed for
testing the method with environmental samples.

*

The authors would like to thank Dr. Lorenzo PERNA and Dr. Laura
ALDAVE DE LAS HERAS for the supportive ideas during the work. The
valuable help of Mr. Ramon CARLOS-MARQUEZ and Ms. Ylva
RANEBO is gratefully acknowledged.

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