Distribution Coefficients of Caesium, Chlorine, Iodine, Niobium, Selenium and Technetium On Olkiluoto Soils

Working Report 2013-68
Distribution Coefficients of Caesium,

Chlorine, Iodine, Niobium, Selenium and
Technetium on Olkiluoto Soils
Mervi Söderlund, Merja Lusa, Sinikka Virtanen,
Ilkka Välimaa, Martti Hakanen, Jukka Lehto
University of Helsinki
Department of Chemistry
Laboratory of Radiochemistry
Anne-Maj Lahdenperä
Saanio & Riekkola Oy
February 2014
Working Reports contain information on work in progress

or pending completion.

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Distribution coefficients of caesium, chlorine, iodine, niobium, selenium

and technetium on Olkiluoto Soils
ABSTRACT
Retention of caesium, chlorine, iodine, niobium, selenium and technetium was
investigated on soil samples from Olkiluoto using laboratory batch sorption
experiments. Distribution coefficients were measured for both dried and sieved and
untreated (wet, not sieved) mineral soil and humus in aerobic and anaerobic conditions.
Mineralogical composition of the samples was determined by XRD-analysis.
Caesium was sorbed efficiently on mineral soil samples and less efficiently on humus.
Sorption decreased with decreasing cation exchange capacity and clay fraction content.
The effect of competing cations decreased in the order Cs+>NH4+>K+>Ca2+>Na+.
Chlorine was not retained by mineral soil samples, and the sorption was weak on
humus.
The sorption of iodine was the strongest on humus and the weakest on the untreated
mineral soil samples in the anaerobic conditions. In the mineral soil samples, the
sorption decreased with decreasing organic matter content and increasing pH.
The retention of niobium on soil samples was the most efficient among the studied
elements. The retention was high regardless of the aeration conditions. Sorption on
humus was smaller.
Selenium was retained efficiently on humus. Sorption on mineral soil samples was
stronger in aerobic conditions. Sorption increased with time.
Technetium was sorbed well on humus and anaerobic, untreated mineral soil samples.
Sorption increased with increasing organic matter content and decreasing redox
potential.
The results from the sorption experiments are used in the site specific radionuclide
migration modelling.
Keywords: Distribution coefficient (Kd), caesium, chlorine, iodine, technetium,
sorption, soil, organic matter.
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3

Cesiumin, kloorin, jodin, niobiumin, seleenin ja teknetiumin

jakaantumiskertoimet Olkiluodon maaperänäytteissä
TIIVISTELMÄ
Cesiumin, kloorin, jodin, niobiumin, seleenin ja teknetiumin pidättymistä Olkiluodon
maaperänäytteisiin tutkittiin laboratoriossa kokeellisissa eräsorptiokokeissa. Maaperä-
näytteet joko kuivattiin ja seulottiin tai käytettiin käsittelemättöminä. Näytteiden mine-
raloginen koostumus määritettiin XRD-analyysillä. Sorptiokokeita tehtiin mineraali-
maa- ja humusnäytteille hapellisissa ja hapettomissa olosuhteissa.
Cesium pidättyi tehokkaasi mineraalimaanäytteisiin ja heikommin humukseen. Sorptio
heikkeni vähenevän kationinvaihtokapasiteetin ja savifraktion funktiona. Kilpailevien
kationien vaikutus pieneni järjestyksessä Cs+>NH4+>K+>Ca2+>Na+.
Kloori ei pidättynyt mineraalinäytteisiin ja sorptio oli heikkoa humukseen.
Jodin sorptio oli voimakkainta humukseen ja heikointa käsittelemättömiin mineraali-
maanäytteisiin hapettomissa olosuhteissa. Mineraalimaassa sorptio väheni orgaanisen
aineksen pitoisuuden vähetessä ja pH:n kasvaessa.
Niobiumin pidättyminen maaperänäytteisiin oli tehokkainta tutkittujen aineiden jou-
kossa. Niobium pidättyi tehokkaasti mineraalinäytteisiin hapellisissa ja hapettomissa
olosuhteissa. Sorptio humusnäytteisiin oli heikompaa.
Seleeni pidättyi tehokkaasti maaperän orgaaniseen ainekseen, kun taas sorptio mine-
raalimaanäytteisiin oli voimakkaampaa hapellisissa olosuhteissa. Sorptio kasvoi ajan
funktiona.
Teknetium pidättyi hyvin käsittelemättömään humukseen ja hapettomiin mineraali-
maanäytteisiin. Sorptio voimistui kasvavan orgaanisen aineksen pitoisuuden ja pienene-
vän redox potentiaalin funktiona.
Sorptiokoetuloksia käytetään radionuklidien paikkakohtaisessa migraatiomallinnuk-
sessa.
Avainsanat: Jakaantumiskerroin (Kd), cesium, kloori, jodi, teknetium, (ad)sorptio,
maaperä, orgaaninen aines.
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TABLE OF CONTENTS
ABSTRACT
TIIVISTELMÄ
1 INTRODUCTION ..................................................................................................... 5
1.1 Posiva’s sorption experiment programme in HYRL .......................................... 5
1.2 Relevance of radionuclides in sorption studies ................................................ 7
1.3 Distribution coefficient Kd ................................................................................. 8
1.4 Overburden properties at Olkiluoto .................................................................. 9
2 MATERIALS .......................................................................................................... 13
2.1 Sampling ........................................................................................................ 13
2.1.1 Sampling locations .................................................................................. 13
2.1.2 General description of soil sampling ....................................................... 14
2.2 Characterisation of the soil samples .............................................................. 23
2.2.1 Chemical characteristics ......................................................................... 23
2.2.2 Geotechnical characteristics ................................................................... 27
2.2.3 Mineralogy............................................................................................... 32
2.3 Water samples ............................................................................................... 34
2.3.1 Soil solution sampling and chemical characteristics ............................... 34
2.3.2 Soil solution simulant .............................................................................. 40
2.3.3 Electrolyte and buffer solutions ............................................................... 40
2.3.4 Radioactive tracers ................................................................................. 41
3 METHODS............................................................................................................. 43
3.1 Analysis of waters .......................................................................................... 43
3.1.1 Cation and anion analysis ....................................................................... 43
3.1.2 pH measurement..................................................................................... 43
3.1.3 Redox potential measurement ................................................................ 43
3.1.4 Tracer activity measurement ................................................................... 44
3.2 Batch sorption studies .................................................................................... 44
3.2.1 Experiment series programme ................................................................ 45
3.2.2 Aerobic soil samples ............................................................................... 48
3.2.3 Anaerobic soil samples ........................................................................... 48
3.2.4 Untreated humus samples ...................................................................... 50
3.2.5 Irradiated humus samples ....................................................................... 50
4 RESULTS .............................................................................................................. 51
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4.1 Kd values for caesium ..................................................................................... 51

4.1.1 Dried and fractioned soil samples of OL-KK14, OL-KK15 and OL-KK16 51
4.1.2 Aerobic untreated soil samples of OL-KK20 and OL-KK21 .................... 55
4.1.3 Anaerobic untreated soil samples of OL-KK20 ....................................... 57
4.1.4 Untreated humus samples of OL-KK21 .................................................. 58
4.1.5 Effect of competing cations on the sorption of caesium .......................... 59
4.1.6 Recommendations of the Kd values for caesium..................................... 64
4.2 Kd values for chlorine ..................................................................................... 66
4.2.1 Aerobic untreated soil samples of OL-KK20 ........................................... 66
4.2.2 Dried and fractioned humus samples of OL-KK15 .................................. 67
4.2.4 Irradiated humus samples of OL-KK21 ................................................... 69
4.2.5 Recommendations of the Kd values for chlorine ..................................... 69
4.3 Kd values for iodine ........................................................................................ 70
4.3.2 Aerobic untreated soil samples of OL-KK20 and OL-KK21 .................... 73
4.3.6 Recommendations of the Kd values for iodine ........................................ 77
4.4 Kd values for niobium ..................................................................................... 79
4.4.4 Recommendations of the Kd values for niobium ..................................... 85
4.5 Kd values for selenium .................................................................................... 86
4.5.4 Recommendations of the Kd values for selenium.................................... 91
4.6 Kd values for technetium ................................................................................ 92
4.6.3 Anaerobic untreated soil samples of OL-KK20 and OL-KK21 ................ 95
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4.6.6 Recommendations of the Kd values for technetium ................................ 98
5 SUMMARY .......................................................................................................... 101
REFERENCES ........................................................................................................... 107
APPENDIX 1. OL-KK20 and OL-KK21 soil pH ........................................................... 123
APPENDIX 2. OL-KK20 and OL-KK21 organic and dry matter content ..................... 124
APPENDIX 3. OL-KK20 and OL-KK21 mineralogy .................................................... 125
APPENDIX 4. OL-KK14, OL-KK20 and OL-KK21 specific surface areas .................. 127
APPENDIX 5. Kd values of caesium ........................................................................... 129
APPENDIX 6. Kd values of chlorine ............................................................................ 136
APPENDIX 7. Kd values of iodine ............................................................................... 138
APPENDIX 8. Kd values of niobium ............................................................................ 142
APPENDIX 9. Kd values of selenium .......................................................................... 145
APPENDIX 10. Kd values of technetium ..................................................................... 148
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1 INTRODUCTION
A KBS-3-type repository for the spent fuel from the Finnish nuclear power reactors in
Olkiluoto and Loviisa is to be built in the bedrock at the Olkiluoto site (Posiva 2009). In
the current repository design, the repository is constructed on a single level and the floor
of the deposition tunnels is at the depth of between 400-450 m in the Olkiluoto bedrock.
The repository programme includes a long-term safety case, where also the potential
radiological impacts on humans and other biota are evaluated (Hjerpe et al. 2010).
The biosphere behaviour evaluation of the radionuclides includes aspects concerning the
migration of radionuclides in soils, sorption on soil particles and transfer from soil to
plants. In the transport modelling calculations, the sorption of radionuclides on the solid
phase is taken into consideration through the radionuclide distribution coefficient (Kd)
value. Kd is dependent upon the element, soil properties and hydrogeochemical
conditions.
The main mineralogical and chemical characteristics of the different soil layers,
including the soil solution, that determine the sorption of radionuclides in the
overburden consist of the type of the clay minerals, clay and organic matter content,
particle size distribution, redox potential and pH. Radionuclides having a high tendency
of forming anionic species in aqueous solutions, such as chlorine, iodine, selenium and
technetium, are weakly sorbed on soil mineral constituents. This leads to high potential
mobility in the overburden. The sink for the anionic radionuclides is typically the
organic matter. On the other hand, cationic radionuclides such as caesium, are sorbed
effectively on the clay minerals. Thus, it is important to understand the behaviour of the
specific elements in the defined soil type, and to be able to evaluate their behaviour in
the future in similar soils based on the current knowledge.
1.1 Posiva’s sorption experiment programme in HYRL
A research project on the overburden migration of long-lived radionuclides originating

from the spent nuclear fuel was launched in the laboratory of Radiochemistry (HYRL)
in 2008. The responsible research director of the “biosphere project” in HYRL is
professor Jukka Lehto. The responsible researchers during the project include MSc.
Mervi Söderlund, MSc. Merja Lusa and Dr. Kaisa Vaaramaa. The research is funded by
Posiva Oy. The coordinating person in Posiva is Ari T. K. Ikonen, and Anne-Maj
Lahdenperä from Saanio & Riekkola Oy is involved as a consult.
The research scope of the biosphere project is to gain information on the safety
assessment of spent nuclear fuel, and especially on the migration of radionuclides in the
biosphere. The behaviour of radionuclides in the chosen material, e.g. soil or mire
samples, is studied in the laboratory by sorption experiments in the circumstances
relevant to the final disposal conditions. Distribution coefficients, Kd values, determined
in the experiments can be used in the modelling of the mobility and migration of
radionuclides. The sorption research includes the steps of sampling and material
characterisation; sorption experiments in the desired conditions e.g. as a function of pH;
the use of computational methods in the planning of the experiments and evaluation of
the results; the speciation analysis of the redox sensitive elements (I and Se) and
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estimation of the effect of speciation on the sorption; analysis, evaluation and reporting
of the results.
By the year 2012, the sorption experiments were mainly done for the Olkiluoto soil
samples. The sorption experiments with the soil samples of a well-developed podzol
soil of an inland reference site will be done on a later occasion, during 2015. With these
samples, fewer tests are to be conducted and the special interest will lie in the eluvial
(leaching) and illuvial (enriching) layers typical of podzols.
In 2011, the first mire samples were taken from Lastensuo in Eurajoki, and their
characterisation is almost complete. The sorption experiments with the mire samples
began in 2012 and are still ongoing. More samples of Posiva’s mire reference sites
(Haapanen et al. 2010) are to be collected, characterised and used in the experiments. In
2014 or 2015, sediment samples are collected of Posiva’s reference lakes (Haapanen et
al. 2010) and from the surface sea sediments in the vicinity of Olkiluoto Island
(Lahdenperä & Keskinen 2011). The sorption experiments with the sea and lake
sediment samples are to be conducted in 2015 and 2016. The research and sampling
schedule of the biosphere project is presented in Table 1.
Table 1. Research and sampling schedule of the Posiva’s biosphere project in HYRL.
Year Soil Mire Lake Sea
sampling of OL-
KK14, OL-KK15 and
2008 OL-KK16 & sorption
experiments with Cs, I
and Tc
sampling of OL-KK20
& sorption
2009 experiments with Cs, I
and Tc
sampling of OL-KK21
& sorption
2010 experiments with Cs,
Cl, I, Nb and Tc
sorption experiments
with I, Mo, Nb, Se and
2011 Tc & speciation
sampling of Lastensuo
analysis of I
with Cs, I, Mo and Nb
2012 & selectivity
with Cs, Cl, I, Se and
Tc
coefficients of Cs
sampling
2013 & sorption
experiments
2014 sorption experiments

sampling sampling
podzol sampling &
2015 sorption experiments & sorption & sorption
experiments experiments
2016 sorption experiments sorption experiments

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1.2 Relevance of radionuclides in sorption studies
In the long-term dose assessment of spent nuclear fuel certain key radionuclides
(elements) have been identified (Hjerpe et al. 2010). These are the nuclides expected to
be transported to the biosphere within the dose assessment window of 10 000 years and
induce the major radiation dose to humans in the biosphere calculation cases.
Key radionuclides are further divided into top priority and high priority radionuclides.
The top priority radionuclides C-14, Cl-36 and I-129, are the ones to dominate the
radiation dose induced to humans in the most realistic biosphere model calculations.
The high priority radionuclides are expected to give a substantial contribution to the
radiation doses in a few calculation cases. The high priority radionuclides include three
subgroups (I-III). Table 2 summarises the radionuclides included in the top and high (I-
III) priority groups in the 2009 dose assessment (Hjerpe et al. 2010); in the forthcoming
assessments, however, some changes are expected (based on the preliminary
information, silver isotope(s) are rising into high priority groups whereas some nuclides
will become less significant).
Table 2. The priority grouping of radionuclides based on their safety relevance in the
long-term safety of spent nuclear fuel (Hjerpe et al. 2010).
Top priority High priority (I) High priority (II) High priority (III)
Mo-93 Ni-59
C-14 Pd-107
Nb-93m Se-79
Cl-36 Sn-126
Nb-94 Sr-90
I-129 Sb-126
Cs-135 Y-90
In the safety assessment, C-14 is handled with specific activity models not requiring Kd
estimates because of its abundance in the biosphere and major role in biochemistry
(Hjerpe et al. 2010). On the other hand, the contribution of fission nuclide I-129 to the
intermediate and high level radioactive waste is significant due to its high yield on the
fission of U-235 and Pu-239 atoms, 0.6 % and 1.6 % respectively, long physical half-
life (1.57x107 y) and high potential mobility in soil (Ashworth et al. 2003; Firestone et
al. 1998; Hu et al. 2005; Robens & Aumann 1988). Like I-129, Cl-36 has long physical
half-life (3.01x105 y) and high mobility in soil, but also high soil-to-plant transfer and
bioavailability (Ashworth & Shaw 2006b; Colle et al. 2005; Firestone et al. 1998;
Sheppard et al. 1996). Cl-36 is formed in the neutron capture of stable Cl-35 by the
reaction 35Cl(n,γ)36Cl in the fuel and surrounding metal parts (Sheppard et al. 1996).
Nb-93m, Nb-94 and Cs-135 are included in the high priority (I) group of radionuclides
in the long-term safety of spent nuclear fuel (Hjerpe et al. 2010). Nb-93m and Nb-94 are
produced in the neutron activation of stable Nb-93 in the metal parts surrounding the
fuel by the reaction Nb-93(n,n)Nb-93m and Nb-93(n,γ)Nb-94, but also in the fission of
U-235 and Pu-239 (fission yields 1.8x10-11 and 2.3x10-10 % for Nb-93m and 9.4x10-4
and 2.5x10-7 % for Nb-94, respectively) (Andersson et al. 1979; Firestone et al. 1998).
The main source of Nb-94 is the activation reaction, but the primary source of Nb-93m
is the decay of Mo-93 (Firestone et al. 1998). The physical half-life of Nb-93m and Nb-
94 are 16.13 and 2.03x104 years, respectively. Unlike previously mentioned
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radionuclides, Cs-135 exist solely in the cationic form (Torstenfelt et al. 1982). Even
so, the importance of Cs-135 in the safety analysis arises from its high yield on the
fission of U-235 (6.5 %) and long physical half-life of 2.3x106 years (Firestone et al.
1998). The migration rate of caesium in soils is very low due to the efficient retention
on clay minerals (Bürmann et al. 1994, Kónya et al. 2005, Zygmunt et al. 1998).
The most important radioisotope of selenium in the spent nuclear is Se-79, which is
classified to the high priority (II) group (Hjerpe et al. 2010). Se-79 is a fission product
and a neutron activation product formed by the reaction Se-78(n,γ)Se-79 from stable Se-
78. It has the physical half-life of 3.77x105 years and high potential mobility in soil due
to its anionic nature (Shaw & Ashworth 2010).
Tc-99 is one of the main fission products formed in the nuclear fission of U-235 and Pu-
239 with a total fission yield of 6.13 % (Ashworth & Shaw 2005; Denys et al. 2003;
Lieser & Bauscher 1987; Sheppard et al. 1983). Because of its high yield, Tc-99 is one
of the most abundant elements in the intermediate and high activity level nuclear waste,
with substantial contribution to the activity level after 100 000 years (Abdelouas et al.
2005; Ashworth & Shaw 2005; Denys et al. 2003; Lieser & Bauscher 1987; Palmer &
Meyer 1981). Tc-99 has been previously presumed to be a major radiation source for
humans along with I-129 because of its long physical half-life (2.13x 105 y) and high
mobility in soil as pertechnetate (TcO4-) ion (Ashworth & Shaw 2005; Denys et al.
2003; Lieser & Bauscher 1987; Palmer & Meyer 1981), but in Posiva’s long-term safety
analysis of spent nuclear fuel Tc-99 has not been a key radionuclide of concern (Hjerpe
et al. 2010) due to its minor release to the biosphere within the 10 000-year dose
assessment time window.
1.3 Distribution coefficient Kd
The sorption of Cs, Cl, I, Nb, Se and Tc to the Olkiluoto soil samples was studied by
batch sorption experiments. The used tracers were Cs-134, Cl-36, I-125, Nb-95, Se-75
and Tc-99. Part of the soil samples were dried and sieved (< 2 mm), whereas others
were untreated (wet, not sieved). Sorption was studied in aerobic and anaerobic
conditions.
The biosphere assessment of the repository long-term safety includes aspects
concerning the migration of radionuclides in soils, sorption to soil particles and transfer
from soil to plants. The distribution coefficient, Kd, is used to describe the retention of
substances on the solid phase. Kd value is defined (e.g. Harjula 2000) as the
concentration ratio of the radionuclide between solid and liquid phases in the
equilibrium state (Equation 1):
[1]
Equation 1. The definition of the distribution coefficient Kd. Cs = concentration of the

element in the solid phase and Cl = concentration of the element in the liquid phase.
High Kd value refers to a considerable retention of radionuclide in soil or sediment
systems and low concentration in the liquid phase, whereas for low Kd values the
retention is weak and radionuclide concentration in solution is high. Kd is widely used
as an indicator of the potential mobility of radionuclides in the environment since at a
given water flow rate the distribution coefficient is proportional to the transport rate of
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the radionuclide. At Kd values ≤0.1 ml/g an element can be considered as mobile as

water, whereas an element with Kd value of ≥10 000 ml/g is practically immobile within
the specified time boundaries (Sheppard et al. 2009b).
High Kd value refers to a considerable retention of radionuclide in soil or sediment
systems and low concentration in the liquid phase, whereas for low Kd values the
retention is weak and radionuclide concentration in solution is high. Kd is widely used
as an indicator of the potential mobility of radionuclides in the environment since at a
given water flow rate the distribution coefficient is proportional to the transport rate of
the radionuclide. At Kd values ≤0.1 ml/g an element can be considered as mobile as
water, whereas an element with Kd value of ≥10 000 ml/g is practically immobile within
the specified time boundaries (Sheppard et al. 2009b).
The most long-lived radionuclides have elongated interaction times with soils ranging
from centuries to millennia. Thus, it has been proposed that desorption Kd values
measured for extracted indigenous stable elements from field moist soils give a more
truthful description of the slow retention processes at steady state conditions (Sheppard
et al. 2009a, 2009b; Sheppard 2011). Slow processes are, for example, the fixation of
caesium on the clay minerals’ frayed edge sites or incorporation of chlorine on organic
matter (Bastviken et al. 2007; Hird et al. 1995). Desorption Kd values of indigenous
elements are typically higher than sorption Kd values of radioactive tracers because of
the longer interaction time with the solid phase and formation of less soluble forms
(Sheppard et al. 2009b). On the other hand, the retention of short-lived radionuclides
may be rather well described by the experimental sorption experiments (Sheppard et al.
2009b; Sheppard 2011).
Kd measured in the batch experiment is dependent on the experimental setup in the
sense that Kd varies as the ambient temperature, rexod conditions, pH, organic matter
content, particle size distribution, presence of competing ions, microbial activity etc.
changes (e.g. Ashworh & Shaw 2006a; Begg et al. 2007; Cha et al. 2006; Gil-García et
al. 2009; Lieser & Bauscher 1987; Sheppard et al. 1990; Sheppard & Thibault 1990;
Zygmunt et al. 1998). All these factors are effective in the natural conditions as well.
Kd values are typically used in the geosphere transport modelling, when the
radionuclide input rates to biosphere are calculated. Radionuclide release rates are, in
turn, used to model the distribution of radionuclides within the biosphere. These
simulations give activity concentrations in environmental media, which are the basis for
evaluating the radiological impacts on humans and biota (Hjerpe & Broed 2010).
1.4 Overburden properties at Olkiluoto
Olkiluoto (Figure 1), a moderately sized island with current surface area of about 12
km2, situates on the eastern coast of the Baltic Sea. The bedrock comprises mostly of
high-grade metamorphic supracrustal rocks (Kärki & Paulamäki 2006). Due to the
continuous post-glacial crustal rebound (“land uplift”), currently at the rate of 6 mm/y
(Eronen et al. 1995; Kahma et al. 2001), about a thousand years ago many of the
initially small islands were interconnected into a bigger island and the Olkiluoto Island
had begun to get its present shape (Mäkiaho 2005). The effects of crustal rebound are
accentuated by a rather flat topography and paludification.
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The bedrock surface at Olkiluoto is quite variable, but the ground surface is rather
smooth even in the places where the bedrock topography changes abruptly. As a result
of the last glaciation, bedrock depressions are filled with a thick layer of overburden.
The current mean elevation on Olkiluoto Island is +5 meters above the sea level, and the
highest points are Liiklankallio (+18 m), Selkänummenharju (+13 m) and
Ulkopäänniemi (+12 m) (Lahdenperä et al. 2005).
Figure 1. Olkiluoto Island. Topographic database, National Land Survey, permission

41/MYY/12 (Layout Posiva Oy/Jani Helin).
The most common soil types on Olkiluoto Island are fine-textured till (53 %), sandy till
(39 %), gravelly till (4 %), peat (3.4 %) and outcrops (0.6 %) (Rautio et al. 2004). The
thickness of the till cover is commonly 2-4 m and it is rich in clay fractions in some
sites (Huhta 2005, 2007, 2009, 2010; Lintinen et al. 2003; Lintinen & Kahelin 2003;
Lahdenperä et al. 2005, Lahdenperä 2009). Some Littorina and Anculys clay areas exist,
in addition, to the areas of recent mud cover, especially on the northern and southern
sides of the island (Haapanen et al. 2009). Soils at Olkiluoto are weakly developed
(Tamminen et al. 2007) due to the short time span of land-uplift and development of 0-
3000 years (Mäkiaho 2005). According to Tamminen et al. (2007), the typical soil types
are undeveloped Arenosols and Regosols, thin or coarse-grained Leptosols and
groundwater-type Gleysols. The predominant soil forming process in Finland is
podsolization (Koljonen 1992), a slow process as the formation of a mature podzol
profile can take up to 500-1500 years (Starr 1991). Typical podzol soil horizons are
weakly developed at Olkiluoto (e.g. Lintinen et al. 2003; Lintinen & Kahelin 2003;
Lahdenperä 2009; Lusa et al. 2009).
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The most common soil types on Olkiluoto Island are fine-textured till (53 %), sandy till
(39 %), gravelly till (4 %), peat (3.4 %) and outcrops (0.6 %) (Rautio et al. 2004). The
thickness of the till cover is commonly 2-4 m and it is rich in clay fractions in some
sites (Huhta 2005, 2007, 2009, 2010; Lintinen et al. 2003; Lintinen & Kahelin 2003;
Lahdenperä et al. 2005, Lahdenperä 2009). Some Littorina and Anculys clay areas exist,
in addition, to the areas of recent mud cover, especially on the northern and southern
sides of the island (Haapanen et al. 2009). Soils at Olkiluoto are weakly developed
(Tamminen et al. 2007) due to the short time span of land-uplift and development of 0-
3000 years (Mäkiaho 2005). According to Tamminen et al. (2007), the typical soil types
are undeveloped Arenosols and Regosols, thin or coarse-grained Leptosols and
groundwater-type Gleysols. The predominant soil forming process in Finland is
podsolization (Koljonen 1992), a slow process as the formation of a mature podzol
profile can take up to 500-1500 years (Starr 1991). Typical podzol soil horizons are
weakly developed at Olkiluoto (e.g. Lintinen et al. 2003; Lintinen & Kahelin 2003;
Lahdenperä 2009; Lusa et al. 2009).
Ca2+, Mg2+, K+, Na+, Al3+ and H+ are the main exchangeable cations in the Olkiluoto
soils (Lahdenperä 2009; Lintinen et al. 2003; Lusa et al. 2009). Surface soils are
naturally acidic and the pH increases with soil depth (Lahdenperä et al. 2005;
Lahdenperä 2009; Lusa et al. 2009). The pH in the humus layer, surface soils and C
layer (unaltered soil material) are typically 3.7-4.4, 4.0-8.0 and 6.5-8.0, respectively
(Lahdenperä 2009; Lusa et al. 2009).
The typical minerals in order of abundance for gravel (Ø > 2 mm), sand (Ø 0.02-2 mm)
and silt fractions (Ø 0.002-0.02 mm) are quartz, plagioclase, potassium feldspar, micas,
chlorite and hornblende (Lintinen et al. 2003; Lusa et al. 2009). Illite, hornblende and
chlorite are the typical minerals in the clay fraction (Ø < 0.002 mm) (Lintinen et al.
2003; Lusa et al. 2009). Specific surface area of soil particles varies between 2.3-15
m2/g and density between 2.8-3.0 g/cm3 (Lintinen & Kahelin 2003; Lintinen et al.
2003).
The results from the recharge computations carried out with the surface hydrology
model indicate that the Olkiluoto bedrock groundwater system is transport-limited,
whereas the overburden is supply-limited. The water supply from the overburden to the
bedrock is higher than the bedrock system can transmit, which is due to the lower
hydraulic conductivity of the bedrock compared with the overburden soils. The supply-
limited overburden groundwater system can result in greater runoff and
evapotranspiration with increased precipitation (Karvonen 2008). The average
groundwater surface usually lies approximately in 2 meters below the ground surface
(Lahdenperä et al. 2005; Lahdenperä 2009; Karvonen 2008, 2009).
12

13

2 MATERIALS
2.1 Sampling
2.1.1 Sampling locations
Soil and soil solution samples were taken from the deep soil pits excavated at the
Olkiluoto Island for the overall characterisation of the overburden at the site. Soil
samples were taken from five soil pits, namely OL-KK14, OL-KK15, OL-KK16, OL-
KK20 and OL-KK21. Soil water and soil samples of OL-KK14, OL-KK15 and OL-
KK16 were taken in May 2008, OL-KK20 in 2009 and OL-KK21 in 2010. The
sampling locations at the Olkiluoto Island are presented in Figure 2. In Table 3 are the
coordinates of the sampling locations according to the Finnish National Coordinate
system (KKJ).
Figure 2. The locations of the excavator pits OL-KK14, OL-KK15, OL-KK16, OL-KK20
and OL-KK21 at the Olkiluoto Island. Topographic database, National Land Survey,
permission 41/MYY/12 (Layout Posiva Oy/Jani Helin).
Table 3. The coordinates of the excavator pits OL-KK14, OL-KK15, OL-KK16, OL-
KK20 and OL-KK21 according to the Finnish National Coordinate System (KKJ).
Coordinates
Excavator pit
N / latitude E / longitude
OL-KK14 6791925 1525630
OL-KK15 6793022 1526567
OL-KK16 6792108 1528024
OL-KK20 6803452 3205461
OL-KK21 6803358 3205299
14

2.1.2 General description of soil sampling
The vertical soil sampling extended from the soil surface to the immediate vicinity of
the bedrock surface. In the sampling of OL-KK20, the bedrock surface was not reached
because groundwater filled the bottom parts of the pit. Humus and mineral soil samples
were taken from the soil pits OL-KK14, OL-KK15, OL-KK16 and OL-KK21, whereas
only mineral soil layers were sampled in OL-KK20. Humus was sampled at three
different locations in the vicinity of OL-KK21. Aerobic mineral soil samples were taken
from all the studied pits, whereas anaerobic samples were taken only from the soil pits
OL-KK20 and OL-KK21. Table 4 presents a summary of the sample depths and the soil
types of the studied excavator pits.
Table 4. A summary of the sampled soil layers, depths, soil types, soil types used in the
Biosphere Description and Assessment and the sample types taken of the excavator pits
OL-KK14, OL-KK15, OL-KK16, OL-KK20 and OL-KK21 at the Olkiluoto Island. Soil
types of OL-KK20 and OL-KK21 are based on the results of the grain size distribution
analysis ordered by Posiva Oy, whereas the soil types of the soil layers of OL-KK14,
OL-KK15 and OL-KK16 are from Lusa et al. (2009).
Soil sample Soil layer Sampling Soil type Soil type in Sample
depth (cm) biosphere type
assessment
humus 0-5 humus humus
medium mineral
MS1 5-20 sandy till
soil aerobic,
medium mineral dried and
OL-KK14 MS2 20-60 sandy till
soil fractioned
medium mineral soil samples
MS3 60-105 sandy till
soil
MS4 105-240 clay clay
medium mineral
MS1 7-50 sand
soil
fine grained aerobic,
MS2 50-80 fine mineral soil dried and
OL-KK15 silty/clayish till
fractioned
MS3 80-110 fine sand fine mineral soil
soil samples
MS4 110-160 clay clay
coarse grained coarse mineral
MS5 160-300
sandy till soil
humus 0-10 humus
coarse mineral
MS1 10-30 coarse sand
soil aerobic,
medium mineral dried and
OL-KK16 MS2 30-50 sand
soil fractioned
fine to coarse fine to coarse soil samples
MS3 50-110
sand mineral soil
medium mineral
MS4 110-300 sand/sandy till
soil
15

Table 4. Continued.
Soil sample Soil layer Sampling Soil type Soil type in Sample
depth (cm) biosphere type
assessment
not medium mineral
70 sandy till
specified soil
not medium mineral
130 sandy till aerobic and
specified soil
anaerobic
medium mineral
OL-KK20 MS2 205 sandy till
soil
untreated
mineral soil
medium mineral samples
MS3 300 sandy till
soil
medium mineral
MS3 340 sandy till
soil
MS1 40 fine sandy till fine mineral soil aerobic
untreated
MS1 110 fine sandy till fine mineral soil
humus
MS1 175 fine sandy till fine mineral soil samples;
OL-KK21 medium mineral aerobic and
MS2 240 sandy till anaerobic
soil
medium mineral untreated
MS3 295 sandy till mineral soil
soil
samples
medium mineral
MS3 360 sandy till
soil
Aerobic soil samples

Aerobic soil samples were taken from all the studied soil pits with a shovel and
conserved in plastic bags. OL-KK14, OL-KK15 and OL-KK16 samples were dried and
sieved into grain sizes <0.063 mm, 0.063-0.125 mm, 0.125-0.25 mm, 0.25-0.50 mm,
0.50-1.0 mm, 1.0-2.0 mm and >2.0 mm at the Geological Survey of Finland. The grain
size fraction <0.063 mm was further analysed at the laboratory of Labtium Oy using
Sedigraph 5100-instrument (Lusa et al. 2009). Untreated samples of OL-KK20 and OL-
KK21 were preserved in plastic bags in the room temperature at the laboratory of
Radiochemistry, the University of Helsinki (Helsingin yliopiston Radiokemian
laboratorio, HYRL).
Figures 3-7 presents the photographs and graphics of the soil profiles OL-KK14, OL-
KK15, OL-KK16, OL-KK20 and OL-KK21. A photo of the humus sampling sites 1, 2
and 3 of OL-KK21 are presented in Figure 8.
16

Figure 3. Soil profile of OL-KK14 (upper picture; by Anne-Maj Lahdenperä/ Saanio &
Riekkola Oy) and soil profile graphic (lower picture; by Teea Penttinen/ Pöyry Finland
Oy).
17

Figure 4. Soil profile of OL-KK15 (by Anne-Maj Lahdenperä/ Saanio & Riekkola Oy)
and soil profile graphic (lower picture; by Teea Penttinen/ Pöyry Finland Oy).
18

Figure 5. Soil profile of OL-KK16 (upper picture; by Anne-Maj Lahdenperä/ Saanio &
Riekkola Oy) and soil profile graphic (lower picture; by Teea Penttinen/ Pöyry Finland
Oy).
19

Figure 6. Soil profile of OL-KK20 (upper pictue; by Sinikka Virtanen/HYRL) and soil
profile graphic (lower picture; by Teea Penttinen/ Pöyry Finland Oy). The black boxes
in the soil profile graphic indicate the sampling depths of Posiva Oy.
20

Figure 7. Soil profile of OL-KK21 (upper picture; by Jani Helin/Posiva Oy) and soil
profile graphic (lower picture; by Teea Penttinen/ Pöyry Finland Oy). The black boxes
in the soil profile graphic indicate the sampling depths of Posiva Oy.
21

Figure 8. The sampling sites of the humus samples 1 (A), 2 (B) and 3 (C) from the
vicinity of OL-KK21 (Photos by Sinikka Virtanen/HYRL). Humus samples 1 and 3 were
taken from the edges of the soil pit OL-KK21, whereas humus sample 2 was from the
vicinity of Olkiluoto main road.
Anaerobic soil samples

Anaerobic soil samples were taken from different mineral soil layers of OL-KK20 and
OL-KK21 in 2009 and 2010. A special sampler designed for the determination of
volatile compounds from soil samples, bought from Eijkelkamp (04.16 Soil coring kit
for chemical soil research) (Figure 9), was used.
Samples were taken into stainless steel tubes (Figure 10), which were closed with PE-
plugs at both ends. Plugs were taped with duct tape to ensure the tightness of the
samples and to prevent the possible oxidation due to air penetration. Tubes were packed
into plastic bags and taped securely. Samples were transported to the laboratory of
Radiochemistry and transferred into nitrogen filled glovebox. The preservation and
further handling of the samples was done in the glovebox. Samples were characterized
and used as untreated (e.g. no drying or sieving).
22

Figure 9. Soil coring equipment used in the sampling of the anaerobic soil samples. The
length of the ruler is 20 cm. (Photo by Mervi Söderlund/HYRL).
Figure 10. Handle, stainless steel sample tube and coring apparatus taken apart and
assembled together (Photos by Mervi Söderlund/HYRL).
23

2.2 Characterisation of the soil samples
The chemical and geotechnical analyses of the soil samples included the determination
of pH, organic matter and dry matter content, cation exchange capacity (CEC) and
mineralogy. Specific surface area was determined for samples of OL-KK14, OL-KK20
and OL-KK21 by nitrogen gas adsorption. Grain size distribution was measured for
samples of OL-KK14, OL-KK15 and OL-KK16. The detailed results from the analysis
of OL-KK14, OL-KK15 and OL-KK16 samples are given in Lahdenperä (2009) and
Lusa et al. (2009) excluding the specific surface area measurements. Only a rewiev of
the main findings is given here. The analysed parameters, methods and standards used
are summarized in Table 5.
Table 5. Analysed parameters from the soil samples, methods and used standards.
Number of
Parameter Unit Method Standard
samples
Milli-Q-water
see Lusa et al.
pH extraction and 14
2009, ISO 10390
CaCl2 extraction
Lost on ignition
Gravimetrically in
(LOI) = organic % CEN 15407 14
550 °C
matter content
Gravimetrically in
Dry matter content % ISO 11465 14
105 °C
Ammonium
Cation exchange
mmol/kg acetate extraction not specified 14
capacity (CEC)
in pH 4.5
X-ray diffraction
Mineralogy ISO 3310/1 11
analyser
Micrometrics
Specific surface Flowsorb
m2/g not specified 35
area instrument – N2
adsorption
2.2.1 Chemical characteristics
Soil pH was measured both in Milli-Q-water and in dilute CaCl2 solution with soil to
liquid ratio 1:1. Samples were stirred for 30 seconds and left to stand for three minutes
(e.g. Lusa et al. 2009). This was repeated five times, after which the samples were let to
settle for ten minutes before pH measurement. A pH test series with the anaerobic soil
sample of OL-KK20 sample depth 0.7 m was conducted both in aerobic and anaerobic
conditions in order to found out if a change in the ambient conditions has a significant
affect on pH. As the pH values showed no dependence upon the measuring conditions
(aerobic/anaerobic), it was decided that the pH values of the anaerobic samples are
measured in the aerobic conditions to simplify the sample treatment and pH measuring.
The pH values of the aerobic and anaerobic soil samples of OL-KK20 and OL-KK21
are given in Appendix 1.
The pH measured in water is typically 0.5-1 pH units higher than in dilute CaCl2 or
other electrolyte solution (Westman 1991). The use of an electrolyte solution induces
lower pH values because Ca2+ and other cations are able to replace part of the acidic
24

cations (e.g. H+, Al3+) present on the soil surfaces’ ion exchange sites into the liquid.
When pure water is used in the pH measurement, the salt concentration of the liquid is
dependent on the readily or easily soluble salts present on the soil surfaces. The
majority of the ions affecting the pH, consisting mainly of H+, are not transferred to the
solution from the ion exchange sites, and thus higher pH values are measured.
The variation in the humus and clay mineral content has the greatest impact on the soil
pH (Birkeland 1984; Kähkönen 1996; Räisänen 1989). The pH typically decreases with
depth as the amount of organic matter and organic acids produced in its decomposition
decreases.
Figure 11 presents the soil pH for the samples of OL-KK14, OL-KK15 and OL-KK16
measured in Milli-Q-water and dilute CaCl2 solution. The pH increases with depth,
having the smallest value in the humus layer, typically 3.5-5.0 in dilute CaCl2 and 4.3-
5.3 in water. In mineral soil layers the pH increases from 4.8 and 5.3 in the uppermost
layers to 7.8 and 8.8 in the bottom soil layers.
The pH remains rather constant throughout the soil pit OL-KK20 (Figure 12). The total
increase in pH is only 0.25 units between the top and bottom soil layers. It is possible
that a systematic error occurred when pH was measured, but a pH measurement from
new samples verified the observation. The pH in the humus layer of OL-KK21 is 5.6
and 6.3 when measured in dilute CaCl2 and Milli-Q-water, respectively. These values
are about two pH units lower compared with the pH values measured for the humus
layers of OL-KK14, OL-KK15 and OL-KK16. In mineral soil layers of OL-KK21 pH
increases with depth from 6.6 and 7.5 to 7.8 and 8.6 as measured in water or CaCl2,
respectively.
OL-KK14 water
0 OL-KK14 CaCl2
OL-KK15 water
50
OL-KK15 CaCl2
OL-KK16 water
OL-KK16 CaCl2
100
Soil depth (cm)
150
200
250
300
3,5 4,0 4,5 5,0 5,5 6,0 6,5 7,0 7,5 8,0 8,5 9,0
Soil pH
Figure 11. The pH of the soil samples of OL-KK14, OL-KK15 and OL-KK16 measured
in Milli-Q-water (Lusa et al. 2009) and dilute CaCl2 solution (Lahdenperä 2009).
25

OL-KK20 water
0 OL-KK20 CaCl2
OL-KK21 water
50 OL-KK21 CaCl2
100
150
Soil depth (cm)
200
250
300
350
400
5,5 6,0 6,5 7,0 7,5 8,0 8,5
Soil pH

Figure 12. The pH of the aerobic soil samples of OL-KK20 and OL-KK21 as measured
in Milli-Q-water and dilute CaCl2 solution.
Figure 13 presents the pH values for the anaerobic OL-KK20 and OL-KK21 soil
samples. The pH increases with depth, and are approximately 0.5 pH units higher than
for the aerobic samples.
OL-KK20 water
0 OL-KK20 CaCl2
OL-KK21 water
50 OL-KK21 CaCl2
100
150
Soil depth (cm)
200
250
300
350
400
6,5 7,0 7,5 8,0 8,5 9,0 9,5
Soil pH
Figure 13. The pH of the anaerobic soil samples of the pits OL-KK20 and OL-KK21 as
measured in Milli-Q-water and dilute CaCl2 solution.
Figure 14 presents the potential cation exchange capacity (CEC) for the soil samples of
OL-KK14, OL-KK15, OL-KK16, OL-KK20 and OL-KK21. Potential CEC indicates
the cation exchange capacity of the soil in a certain, specified pH value, such as 4.5 or
7, determined by buffered salt solutions (Brady & Weil 2002). Effective cation
exchange capacity is determined by neutral salt solutions, such as NH4Cl, in the soil’s
own pH. The potential CECs for OL-KK14, OL-KK15 and OL-KK16 samples were
26

calculated as a sum of Na, K, Mg and Ca ions extracted by 1 M NH4Ac solution in pH

4.5 (Lahdenperä 2009). For OL-KK20 and OL-KK21 soil samples same method was
used with solid to liquid ratio 1:5. Stable Na, K, Mg and Ca concentrations were
measured with ICP-MS (inductively coupled plasma mass spectrometry). Al3+ and Fe2+
were omitted in the calculation of CEC because their concentration was below the limit
of detection of ICP-MS (Table 6).
Table 6. The detection limits for Na, K, Mg, Ca, Al and Fe on ICP-MS.
Detection limit Detection limit
Element Element
(µg/l) (µg/l)
Sodium (Na) 19.9 Calcium (Ca) 59.6
Potassium (K) 115.9 Aluminium (Al) 3.7
Magnesium (Mg) 0.7 Iron (Fe) 3.7

The highest CECs are typically found in the humus layers where the high concentrations
of ion exchange groups, especially –COOH groups, are found in the organic matter
creating CEC capacities as high as 1500-5000 mmol H+/kg dry weight (Birkeland
1984). Typically in mineral soil CEC increases with increasing clay mineral and clay
fraction content. For the soil pits OL-KK14 and OL-KK15 the CEC of the uppermost
mineral soil layer (MS1) was lower than the CEC of the underlying mineral soil layer
(MS2) due to the higher clay fraction in MS2. In the bottom soil layers the CEC
decreased with depth. In the pits OL-KK20 and OL-KK21 CECs varied considerable
between the sampling depths, and there was no clear dependence between CEC and the
soil depth. In OL-KK20, the CEC for the uppermost sampling depth 0.7 m (40
mmol/kg) was the lowest among the studied sampling depths, and the highest value was
calculated for the underlying sampling depth 1.30 m (68 mmol/kg). In OL-KK21, the
CEC was the highest at 1.75 m depth (124 mmol/kg) and the lowest at 1.1 m depth (32
mmol/kg). The CECs of the humus samples taken from the vicinity of OL-KK21 ranged
from 130 mmol/kg to 282 mmol/kg.
Calcium was the main exchangeable cation on soil surfaces followed by magnesium and
sodium. Potassium concentration in the extraction solution was the smallest among the
measured cations indicating relatively low concentration on soil sorption sites. The
reported main exchangeable cations in the Olkiluoto soils are Ca2+, Mg2+, K+, Na+, Al3+
and H+ (Lahdenperä 2009; Lintinen et al. 2003; Lusa et al. 2009).
Table 7 presents the cation exchange capacities for the samples taken of OL-KK20 and
OL-KK21 calculated as a sum of Na, K, Mg and Ca ions extracted by 1 M NH4Cl
solution buffered in pH 4.5.
27

OL-KK14
OL-KK15
0 OL-KK16
OL-KK20
50 OL-KK21
100
Soil depth (cm)
150
200
250
300
350
400
0 100 200 300 400
CEC (mmol/kg)

Figure 14. The potential cation exchange capacities (CECs) for the soil samples of OL-
KK14, OL-KK15 and OL-KK16 (Lahdenperä 2009), OL-KK20 and OL-KK21
calculated as a sum of Na, K, Mg and Ca ion concentrations in 1 M NH4Ac extraction
solution.
Table 7. The potential cation exchange capacity (CEC, mmol/kg of the dry weight) in
the soil samples of OL-KK20 and OL-KK21 determined by NH4Ac buffered in pH 4.5.
CEC was calculated as a sum of Na, K, Mg and Ca ions.
OL-KK20 OL-KK21
Soil depth (cm) CEC (mmol/kg) Soil depth (cm) CEC (mmol/kg)
(standard deviation) (standard deviation)
70 40 (1) 12 (humus 1) 282 (9)
130 68 (-) 12 (humus 2) 130 (3)
205 51 (2) 12 (humus 3) 207 (2)
300 60 (4) 40 43 (1)
340 66 (2) 110 32 (5)
175 124 (69)
240 43 (3)
295 43 (4)
360 56 (1)
- standard deviation was not calculated because the CEC value is based on the Na, K, Mg and Ca
concentrations determined from one soil sample
2.2.2 Geotechnical characteristics
Organic and dry matter content was determined from all the soil samples. Specific
surface area was measured for the samples of OL-KK14, OL-KK20 and OL-KK21. The
results of the organic and dry matter contents of OL-KK14, OL-KK15 and OL-KK16
are presented in Lusa et al. (2009). The results of these soil pits are only reviewed here.
28

Grain size distribution was determined from the soil samples of OL-KK20 and OL-
KK21 in the Laboratory of ALS, Luleå, Sweden, but the sampling depths were
somewhat different than used in the sorption studies. Thus, the analysis results form the
grain size distribution are not presented in this report.
The dry and organic matter content was determined by weighting three to five grams of
humus or soil sample into a beaker glass. The beakers were placed to a drying oven at
the temperature of 105 °C for 24 hours. Samples were cooled to room temperature and
weighted to define the amount of water. The amount of organic matter was determined
as a loss of ignition (LOI) by incinerating the samples in an oven at 550 °C degrees from
five to six hours. After incineration the samples were cooled to room temperature and
weighted. The dry and organic matter content of the samples were calculated using
Equation 2 and 3.
% 100% [2]
Equation 2. The calculation of the dry matter content. m20 = sample mass in room
temperature and m105 = sample mass after annealing at 105°C.
% 100% [3]
Equation 3. The calculation of the organic matter content. morg = mass of the organic
matter in the sample and m550 = the sample mass after annealing at 550 °C.
The organic matter (OM) content decreases rapidly below the humus layer in the
mineral soil layers underneath (Figure 15, Appendix 2). In the humus layer of OL-
KK14, OL-KK15 and OL-KK16 the organic matter content was 59 %, 63 % and 54 %,
respectively, whereas in OL-KK21 the corresponding values were 11 %, 14 % and 10 %
for humus samples 1, 2 and 3. The humus layer of OL-KK21 was very thin and had
considerable amounts of mineral matter mixed up, descriptive of an uppermost mineral
soil layer enriched with organic matter (Ah). This might explain the low organic matter
content of the OL-KK21 humus samples. Instead of humus, the layer might be
representative of an uppermost mineral soil layer enriched with organic matter (Ah). In
the mineral soil layers organic matter content was <1 %.
The dry matter content of the mineral soil samples of OL-KK14, OL-KK15, OL-KK16,
OL-KK20 and OL-KK21 is presented in Figure 16 and for the aerobic and anaerobic
soil samples of OL-KK20 and OL-KK21 in Appendix 2. The dry matter content for the
humus samples of OL-KK14, OL-KK15 and OL-KK16 was 48 %, 43 % and 27 %,
respectively. For the OL-KK21 humus samples 1, 2 and 3 the dry matter content was
29 %, 34 % and 39 %. Figure 17 presents the organic matter (OM) content for the
anaerobic mineral soil samples of OL-KK20 and OL-KK21. The OM contents were
similar to the aerobic samples, but the dry matter content was typically 1.5-3.0 % higher
for the anaerobic samples.
29

OL-KK14
0 OL-KK15
OL-KK16
50 OL-KK20
OL-KK21
100
150
Soil depth (cm)
200
250
300
350
400
0,0 0,5 1,0 1,5 2,0 2,5 3,0
Organic matter content (%)

Figure 15. The organic matter content for the aerobic mineral soil samples of the
excavator pits OL-KK14, OL-KK15 and OL-KK16 (Lusa et al. 2009), OL-KK20 and
OL-KK21.
OL-KK14
OL-KK15
0
OL-KK16
OL-KK20
50
OL-KK21
100
150
Soil depth (cm)
200
250
300
350
400
84 86 88 90 92 94 96
Dry matter content (%)

Figure 16. The dry matter content for the aerobic soil samples of the excavator pits OL-
KK14, OL-KK15 and OL-KK16 (Lusa et al. 2009), and OL-KK20 and OL-KK21.
30

50
100 OL-KK20
OL-KK21
150
Soil depth (m)
200
250
300
350
400
0,4 0,6 0,8 1,0 1,2 1,4
Organic matter content (%)
Figure 17. The organic matter content for the anaerobic mineral soil samples of the
excavator pits OL-KK20 and OL-KK21.
Specific surface areas were determined from the sieved mineral soil samples of OL-
KK14, and bulk soil samples of OL-KK20 and OL-KK21. Samples were sent to the
Tampere University of Technology, where the measurements were done using
Micromeritics Flowsorb instrument. Soil samples were dried to constant weight, cooled
to room temperature and specific surface area was measured based on nitrogen
adsorption (BET/N2). Results for specific surface area measurements are presented in
Figures 18 and 19 and Appendix 3.
For OL-KK14, the specific surface area was the lowest in the topmost mineral soil layer
(MS1 at the depth of 20 cm) ranging from 2.1 to 0.6 m2/g, and the highest, 9.0 and 4.6
m2/g, in the mineral soil layer underneath (MS2 at the depth of 60 cm). Also, the CEC is
higher for MS2 layer than for MS1 (Figure 14) (Lusa et al. 2009). Grain size did not
have a great impact on the specific surface area except for the smallest grain size
fraction, <0.063 mm, were the highest values were seen in every soil layer among the
studied grain size fractions. These results are in a good agreement with the previous
measurements of the specific surface areas of soil particles, even though the smallest
values are below earlier results from Olkiluoto (2.3-15 m2/g) (Lintinen & Kahelin 2003;
Lintinen et al. 2003).
The specific surface area of the OL-KK20 and OL-KK21 samples decreases with
sample depth (Figure 19) from 7 m2/g at 0.7 m depth to 1 m2/g at 3.4 m depth and from
4 m2/g at 0.4 m depth to 1 m2/g at 3.6 m depth. This may be attributed to the formation
of large specific surface area secondary (clay) minerals and weakly crystalline
aluminium and iron oxides as the weathering products of the soil primary minerals
(Birkeland 1984; Brady & Weil 2002). The weathering processes mainly take place in
the uppermost mineral soil layers underneath the humus layer, where hydration,
hydrolysis, acid reactions and oxidation-reduction reactions act simultaneously
changing the soil geological material. Also, the soil texture has an impact on the
specific surface area due to the fact that the particle surface area increases with
decreasing particle size (Brady & Weil 2002).
31

soil depth:
9
5-20 cm
8 20-60 cm
60-105 cm
105-240 cm
Specific surface area (m /g)

7
2
6
0
<0.063 0.063-0.125 0.125-0.25 0.25-0.5 0.5-1.0 1.0-2.0
Grain size (mm)

Figure 18. The specific surface areas of the MS1, MS2, MS3 and MS4 samples of OL-
KK14 as a function of the grain size. The specific surface area was measured by
nitrogen adsorption.
OL-KK20
0 OL-KK21
50
100
150
Soil depth (cm)
200
250
300
350
400
0 1 2 3 4 5 6 7
2
Specific surface area (m /g)

Figure 19. The specific surface area of the soil samples of OL-KK20 and OL-KK21
measured by nitrogen adsorption.
When the distribution coefficients of radionuclides are determined for bedrock samples,
the samples are typically ground and Kd values are determined for a specific grain size
fraction. In this case the correct way to present the Kd values is to normalize to the
specific surface area, because mass based Kd value typically increase with decreasing
grain size fraction. In the case of soil samples, the samples are dry sieved into different
grain size fractions or conserved untreated. Thus, no grinding is involved in the sample
treatment and mass based Kd values determined in the sorption tests give an accurate
picture of the distribution of the radionuclide between the liquid and solid phases. In the
32

following Chapters, the presented Kd values are mass based values and normalisation to
the specific surface area was not carried out.
2.2.3 Mineralogy
Mineralogical analyses of the soil samples of OL-KK20 and OL-KK21 were done in the
Geological Survey of Finland. The samples were dried and grain size fractions <0.01
mm and 1.0-2.0 mm were separated from the bulk sample by sieving. Mineral
composition was examined by X-ray diffraction (XRD) using Philips X’Pert MPD
instrument. XRD spectra were recorded in angle interval 2-70°2θ with step size 0.02°.
Time per step was 1 s. Based on XRD-analysis, IR-spectra was measured for two
samples in accordance to identify kaolinite, chlorite and other clay minerals present in
samples. Swelling clay minerals were determined by heating four samples in 550 °C for
one hour, after which XRD spectra was rerecorded in angle interval 2-35°.
Samples were mainly composed of quartz, potassium feldspar, plagioclase and

kaolinite. Quartz was the main mineral, followed by plagioclase. Some samples
contained minor amounts of micas, amphibole, hematite and chlorite. No swelling clay
minerals were found in the samples. The mineralogy was similar to <0.01 mm and 1.0-
2.0 mm samples differing only in the mineral proportions. The abundance of clay
minerals was higher for the smaller grain size fraction. Difference with regard to the
mineralogical composition of the soil samples of OL-KK14, OL-KK15 and OL-KK16,
amphibole was not one of the main minerals and kaolinite content was much higher.
Figures 20-23 present the main mineral compositions of grain size fractions <0.01 mm
and 1.0-2.0 mm samples separated from bulk soil samples of soil pits OL-KK20 and
OL-KK21. Mineralogy of OL-KK20 and OL-KK21 is given in Appendix 4.
Other
minerals
50 Kaolinite
Plagioclase
100 Potassium
feldspar
150
Quartz
Soil depth (cm)
200
250
300
350
0 10 20 30 40 50 60 70 80 90 100
Mineral content (%)
Figure 20. Quartz, potassium feldspar, plagioclase, kaolinite and other mineral (micas,
amphibole, hematite and chlorite) content for mineral soil samples in the grain size
fraction <0.01 mm of OL-KK20.
33

Other
minerals
50
Kaolinite
Plagioclase
100 Potassium
feldspar
150 Quartz
Soil depth (cm)
200
250
300
350
0 10 20 30 40 50 60 70 80 90 100
Mineral content (%)

fraction 1.0-2.0 mm of OL-KK20.
Other
minerals
Kaolinite
50
Plagioclase
100
Potassium
feldspar
150
Quartz
Soil depth (cm)
200
250
300
350
0 10 20 30 40 50 60 70 80 90 100
Mineral content (%)

fraction <0.01 mm of OL-KK21.
34

Other
minerals
Kaolinite
50 Plagioclase
Potassium
100 feldspar
Quartz
150
Soil depth (cm)
200
250
300
350
0 10 20 30 40 50 60 70 80 90 100
Mineral content (%)

fraction 1.0-2.0 mm of OL-KK21.
2.3 Water samples
The sorption of radionuclides is usually examined in two-component electrolyte

solutions, such as NaCl or CaCl2. For the direct use of the determined Kd values, it is
recommended to use a liquid phase representing the site-specific composition of soil
solution or groundwater to simulate the circumstances on the field conditions (Camps et
al. 2003; Sauvé et al. 2000; Yasuda et al. 1995). To create a suitable composition of the
liquid phase to be used in the sorption tests, it is important to gain knowledge on the soil
solution composition on Olkiluoto Island. Therefore soil solution samples for the main
cation and anion analysis were taken from humus and mineral soil layers of OL-KK14,
OL-KK15 and OL-KK16 in 2008. The pH, DOC, anion and cation analysis results have
been reported previously for two forest intensive monitoring plots of OL-FIP4 (Scots
pine forest) and OL-FIP10 (Norway spruce forest) (Haapanen 2006, 2007, 2008, 2009).
Soil solution analysis results formed the basis for the composition of the soil solution
simulant.
2.3.1 Soil solution sampling and chemical characteristics
Soil solution samples were taken from the soil layers of OL-KK14, OL-KK15 and OL-
KK16. Sampling for soil solution separation was done by inserting a weighted plastic
tube with an inner diameter of 4.6 cm into the wall of the excavator pit at the desired
depths. Soil filled tubes were frozen and sent to the Finnish Forest Research Institute
(Metla, Rovaniemi) for soil solution separation with high speed centrifuge. The pH and
DOC concentration was measured at Metla, whereas the cation and anion analyses were
performed at the Department of Geography (the University of Helsinki). The detailed
35

description of the soil solution sampling and analysis results is presented in Lusa et al.
(2009).
Soil solution sampling of the forest intensive monitoring plots OL-FIP4 and OL-FIP10
was started in 2004 and 2007 (Aro et al. 2010). Samples were taken from different
depths down the soil profile to approximately 30 cm with suction cup lysimeters
(tension lysimetre) installed in the mineral soil layers, and plate lysimeters (zero-tension
lysimetre) typically situated immediately underneath the humus layer. The pretreatment
of the water samples was done in the field and the chemical analyses were done at
Metla, Rovaniemi.
Figure 24 presents the compilation of the average soil and soil solution pH values as a
function of soil depth. Soil pH values were calculated based on the pH values
determined for the aerobic soil samples of OL-KK14, OL-KK15, OL-KK16, OL-KK20
and OL-KK21 (original pictures Figures 11 and 12), whereas soil solution pH values
were based on the pH values for OL-KK14, OL-KK15, OL-KK16, OL-FIP4 and OL-
FIP10 (Figure 25).
soil solution
0 soil; water
soil; CaCl2
50
100
150
Soil depth (cm)
200
250
300
350
400
4,0 4,5 5,0 5,5 6,0 6,5 7,0 7,5 8,0 8,5
pH
Figure 24. The average pH values of the soil and soil solution samples as a function of
soil depth. Soil pH was determined in Milli-Q-water and in dilute CaCl2 solution.
Figure 25 and 26 presents the pH and DOC concentration of soil water and soil solution
samples. The solution pH increases with depth from approximately 4 in the topmost soil
layers (humus) to 7.5 in the deepest mineral soil layers. DOC concentrations reach the
highest values, 120-160 mg/l in the uppermost soil layers (humus) and decrease rapidly
with depth to circa 5 mg/l.
36

OL-KK14
0 OL-KK15
OL-KK16
50
FIP4
FIP10
100
Soil depth (cm)
150
200
250
300
3,5 4,0 4,5 5,0 5,5 6,0 6,5 7,0 7,5 8,0
pH
Figure 25.The pH of the soil water samples (OL-KK14, OL-KK15 and OL-KK16) and
the soil solution samples (Haapanen 2006, 2007, 2008, 2009).

50
OL-KK14
OL-KK15
100 OL-KK16
FIP4
Soil depth (cm)
150 FIP10
200
250
300
0 20 40 60 80 100 120 140 160 180

DOC (mg/l)

Figure 26. The DOC concentration of the soil water samples (OL-KK14, OL-KK15 and
OL-KK16) and the soil solution samples (Haapanen 2006, 2007, 2008, 2009).
The cation (Na, K, Ca and Mg) concentrations of OL-KK14, OL-KK15, OL-KK16, OL-
FIP4 and OL-FIP10 soil solution samples are presented in Figure 27. The main cation
concentrations varied between the samples and depths. In the OL-FIP10, the maximum
sodium concentration was found in the 30 cm depth, 17.5 mg/l, and the minimum
concentration in MS2 of OL-KK14, 1.5 mg/l. Potassium concentrations seem to behave
somewhat similarly, as the highest values were in the humus layers and lowest in the
37

uppermost mineral soil layers. Calcium concentrations varied greatly between the study
sites. The highest Ca concentration was in the humus layer of OL-KK16 (25 mg/l), and
the lowest in MS2 mineral soil layer of OL-KK14 (1.7 mg/l). The maximum and
minimum concentration of magnesium was in MS2 layer of OL-KK15 (11.5 mg/l) and
OL-KK14 (0.6 mg/l), respectively (Haapanen 2006, 2007, 2008, 2009; Lusa et al.
2009). Cation concentrations from the soil solution were measured with ICP-MS.
The main anion (Cl, NO3, F and SO4) concentrations of OL-KK14, OL-KK15, OL-
KK16, OL-FIP4 and OL-FIP10 soil solution samples are presented in Figure 28.
Chloride and nitrate concentrations depended on the sampling depth; decreasing with
increasing soil depth. The highest concentrations for Cl and NO3 were in the humus
layer, 58 mg/l in OL-KK15 and 7.4 mg/l in OL-KK16, respectively. The minimum
chloride concentration 2 mg/l was in the uppermost sampling depth of OL-FIP4 and
OL-FIP10, and in MS2 layer of OL-KK14. Nitrate concentration was typically below 1
mg/l in all the studied sampling depths. The average fluoride concentration in the soil
water samples of OL-KK14, OL-KK15 and OL-KK16 was 2.92 mg/l. The highest
concentration was in the humus sample of OL-KK15 (8.3 mg/l), and the lowest in the
OL-KK16 (0.8 mg/l). Sulphate concentrations varied greatly, the lowest concentration
was only 0.6 mg/l in the uppermost sample of OL-FIP4, and the highest 204 mg/l in
MS2 layer of OL-KK15. Anion concentrations from the soil solution were measured
with ion chromatography (IC).
38

38
Figure 27. Concentrations of the main cations sodium (Na), potassium (K), magnesium (Mg) and calcium (Ca) in the soil solution samples
of OL-KK14, OL-KK15 and OL-KK16 (Lusa et al. 2009) and forest intensive monitoring plots OL-FIP4 and OL-FIP10 (Haapanen 2006,
2007, 2008, 2009).
39

39
Figure 28. Concentrations of the main anions chloride (Cl), fluoride (F), nitrate (NO3) and sulphate (SO4) in the soil solution samples of
OL-KK14, OL-KK15 and OL-KK16 (Lusa et al. 2009) and forest intensive monitoring plots OL-FIP4 and OL-FIP10 (Haapanen 2006,
2007, 2008, 2009).
40

2.3.2 Soil solution simulant
The liquid phase used in the sorption experiments was synthetic soil solution simulant.
The soil solution simulant was composed after the cation and anion analysis of the soil
solution samples taken from the humus and mineral soil layers of OL-KK14, OL-KK15
and OL-KK16 and from the forest intensive monitoring plots OL-FIP4 and OL-FIP10
(Haapanen 2006, 2007, 2008, 2009; Lusa et al. 2009).
Cations in the soil solution simulant were sodium (Na+), potassium (K+), calcium (Ca2+)
and magnesium (Mg2+). The cation concentration was equilibrated with counter anions
chloride (Cl-), sulphate (SO42-) and silicate (SiO32-). Fluoride (F-), nitrate (NO3-) and
phosphate (PO43-) were omitted from the soil solution simulant due to their small
concentrations in the soil solution samples compared with chloride and sulphate
(Haapanen 2006, 2007, 2008, 2009; Lusa et al. 2009).
The soil solution simulant was prepared from J.T. Baker and Merck p.a. and Suprapur
grade chemicals using ultrapure 18 MΩ Milli-Q water. Table 8 presents the reagents
used in the preparation of the soil solution simulant and calculated concentrations of the
cations and anions.
Table 8. The reagents used in the preparation of the soil solution simulant and the
calculated concentrations of the ions.
Ion Reagent Calculated Calculated
concentration concentration
(mg/l) (mmol/l)
Na+ Na2SiO3 x 9 H2O 4.0 0.17
K+ KCl 2.7 0.07
Mg2+ MgSO4 x 7 H2O 2.7 0.11
Ca2+ CaCl2 x 2 H2O 6.5 0.16
SiO32- Na2SiO3 x 9 H2O 6.6 0.08
Cl- KCl and CaCl2 x 2 H2O 16.5 0.36
SO42- MgSO4 x 7 H2O 10.7 0.11
2.3.3 Electrolyte and buffer solutions
CsCl, NaCl, KCl, NH4Cl and CaCl2 electrolyte solutions were used in the sorption
experiments of caesium when the effect of competing cations was investigated. The
cation concentrations of CsCl solutions used were 0.01, 0.1, 1 and 10 mM, whereas the
cation concentrations of other electrolyte solutions were 0.1, 1.0, 10, 100 and 1000 mM.
Electrolyte solutions were prepared from Merck and Riedel-de Häen p.a. and Suprapur
grade reagents in ultrapure 18 MΩ Milli-Q water.
CHES buffer solution (2-(cyclohexylamino)ethanesulfonic acid) was used in the
sorption experiments of Nb-95 in the anaerobic conditions to buffer the solution pH to
9-10. CHES concentration in the final solution was 1.0x10-3 M. CHES was purchased
from Fluka (ultra purity).
41

2.3.4 Radioactive tracers
Radioactive tracers used in the sorption studies were commercially available Cs-134,
Cl-36, I-125, Nb-95, Se-75 and Tc-99.
The initial chemical form of Cs-134 was caesium chloride (CsCl) in 0.1 M HCl. The
tracer was bought from Eckert & Ziegler. Solution for the sorption experiments was
prepared from the stock tracer solution by diluting with 2x10-4 M HCl and by later on
with ultrapure 18 MΩ Milli-Q-water and used without pH adjustment.
The initial chemical form of Cl-36 was sodium chloride (NaCl) in aqueous solution.
The tracer was bought from Amersham Biosciences. Solution for the sorption
experiments was prepared from the tracer stock solution by diluting with ultrapure 18
MΩ Milli-Q-water and used without pH adjustment.
The initial chemical form of I-125 was sodium iodide (NaI) in phosphate buffer
solution. The tracer was bought from MAP Medical Technologies. Solution for the
sorption experiments was prepared from the tracer stock solution by diluting with
ultrapure 18 MΩ Milli-Q-water and used without pH adjustment.
The initial chemical form of Nb-95 was niobium chloride (NbCl5) in 6.0 M HCl. The
tracer was bought from Perkin Elmer as a mixture of Nb-95 and its mother nuclide Zr-
95. Nb-95 and Zr-95 have similar x-ray and γ-energies, for which reason Nb-95 had to
be separated from its mother nuclide Zr-95. The separation was done by the following
scheme (Weiss et al. 1987):
 A small volume (100-300 µl) of Nb-95/Zr-95 solution was drawn via 0.8
injection needle into 1 ml syringe, and the syringe was emptied into a 25 ml
beaker glass. Tracer solution was evaporated to near dryness and dissolved to
0.5-1.0 ml of 10 M HNO3. This procedure was repeated three times.
 The separation column was made of 5 ml syringe by inserting seven layers of

Whatman GF6 glass fibre filters on to the other. A plastic tube was jointed to a
plastic faucet and the faucet was attached to the syringe. The column was pre-
conditioned by withdrawing 2x1 ml of 10 M HNO3 slowly through the filters
into a 5 ml syringe connected to the plastic tube.
 Tracer solution, 1 ml of HNO3 containing Nb-95 and Zr-95, was transferred into
the column. The solution was drawn into a clean 5 ml syringe. The beaker glass
was rinsed with 1 ml of 10 M HNO3 and the acid was transferred to the column
and drawn slowly to the syringe. The solution was moved to a weighted 20 ml
plastic liquid scintillation bottle. This solution was so called ‘absorption
solution’ and contained the majority of the mother nuclide Zr-95.
 The column was washed with 2x1 ml of HNO3 to ensure that all of the non-
sorbed Zr-95 had come through. After this stage, the plastic tube was changed to
a clean one and Nb-95 was eluted from the column with 2x1 ml of 0.5 M HNO3
+ 0.3 M HF solution. The elution solution containing Nb-95 was withdrawn into
a 10 ml syringe and transferred to a weighted 20 ml plastic liquid scintillation
bottle or to a clean 20 ml beaker glass for the change of the tracer matrix from
42

0.5 M HNO3 + 0.3 M HF to 0.1 M HCl. The tracer matrix was changed by
evaporating the solution until dry and dissolving the precipitate into 1 ml of 0.1
M HCl. This procedure was repeated three times, after which the solution was
transferred to a weighted 20 ml (HD PE) plastic liquid scintillation bottle. The
bottle was weighted again to find out the volume of Nb-95 tracer solution. The
purity of the Nb-95 tracer solution was ensured with gammaspectrometry.
The initial chemical form of Se-75 was selenious acid (H2SeO3) in 0.1 M HCl. The
tracer was bought from Eckert & Ziegler. Solution for the sorption experiments was
prepared from the tracer stock solution by diluting with 0.1 M HCl and used without pH
adjustment.
The initial chemical form of Tc-99 was 0.01 M ammonium pertechnetate (NH4TcO4).
The tracer was bought from Amersham International. Solution for the sorption
experiments was prepared from the tracer stock solution by diluting with 0.01 M
NH4OH and used without pH adjustment.
43

3 METHODS
3.1 Analysis of waters
3.1.1 Cation and anion analysis
Cation and anion analysis were conducted to the soil solution samples separated at
Metla and soil solution simulant test samples at the beginning of the sorption
experiments. Analysis of the soil solution samples was conducted in order to find out
the main cations and anions present in the samples. Based on the results, the
composition of the soil solution simulant was created. The required contact time for the
liquid phase to reach a steady-state with the solid state for the main ion composition and
pH was characterised by measuring the changes as a function of time.
From the soil solution samples the main cations Na, K, Ca, Mg and the trace cations Al,
As, Cd, Cr, Cs, Cu, Fe, Mn, Ni, S, Pb, Zn and U were analyzed with Agilent 7500ce/cx
ICP-MS equipped with octopole reaction chamber. Anions F, Cl, NO3, PO4 and SO4
were measured with IC (Metrohm MIC-12 ion chromatogram and ASupp5/100
column). Elemental concentration standards and background (Milli-Q-water) samples
were measured together with the solution samples.
For the soil solution simulant test samples, only Na, K, Ca and Mg were analysed from
the cations, and Cl, SiO3 and SO4 were measured from the anions.
3.1.2 pH measurement
Equilibrium pH was measured from every sorption sample and soil solution simulant
test samples. Before measurements, pH electrode was calibrated with pH buffer
standards (Orion) 4.01, 7.00 and 10.01 and the slope-value was recorded. After
calibration pH electrode was inserted into the solution and the pH value was let to
stabilise. For the aerobic samples, pH was mainly measured from filtered liquid samples
and from some unfiltered, centrifuged samples. In the anaerobic conditions, pH was
solely measured from the unfiltered liquid samples. Gel-filled low maintenance
electrode Orion 9107BNMD was used in the aerobic conditions. In the nitrogen
atmosphere (glovebox), glass electrode Orion 9104APWP was applied.
The pH of the soil solution simulant test samples was determined after the soil and soil
solution simulant reached the steady-state.
3.1.3 Redox potential measurement
Redox potential was measured from the anaerobic sorption samples in the nitrogen
atmosphere of the glovebox. Eh-electrode (Orion 9778BNWP) was calibrated with
ORP-solution (Orion) to correlate the measured values to the corresponding Eh mV
(millivolt) values given by standard/normal hydrogen electrode (SHE or NHE). After
calibration, Eh-electrode was inserted into the soil/water mixture and the redox potential
was let to stabilize. During the Eh-measurement, samples were gently shaken.
Stabilisation was usually achieved in 30-45 minutes.
44

3.1.4 Tracer activity measurement
The tracer activity in the liquid phase was determined by gammaspectrometry or liquid
scintillation counting depending on the radiation properties of the studied nuclide.
The activity of the β- -emitters Cl-36 and Tc-99 was determined by liquid scintillation
counting with 1219 Rackbeta (LKB Wallac) or TriCarb 2910TR (PerkinElmer).
Equilibrium activity was measured from the sorption samples as follows: 8 ml aliquot of
filtered liquid was pipetted into a 20 ml plastic scintillation bottle. 12 ml of scintillation
cocktail (PerkinElmer‘s Optiphase ’Hisafe’ 3 or Ultima Gold AB) was added, and the
bottle was gently shaken to ensure the mixing of the phases. Activity counting samples
were taken to the scintillation counter and let to stabilize from 0.5 hours to 12 hours
before the counting to avoid uncertainties created by the presence of air bubbles.
Simultaneously with the sorption samples, tracer standards and Milli-Q water
background samples. Equation 4 was used to calculate the sample Kd value. All the Kd
values were based on the sample dry weight and are thus comparable with each other.
[4]
Equation 4. The calculation of the Kd value. Ai = measured initial activity (ie. the
activity of the tracer standard), Af = measured final activity of the solution, Vams =
volume (ml) of the activity measurement sample, Vi = initial volume (ml) of the sample
and m = dry mass (g) of the sample.
The γ–emitters Cs-134, I-125, Nb-95 and Se-75 were measured by gammaspectrometry
with Wizard™ 3” (PerkinElmer Wallac). The tracer final activity in the liquid phase
was determined from the sorption samples by pipetting 10 or 15 ml of centrifuged (Nb-
95 and Se-75) or typically filtered liquid into a 20 ml plastic scintillation bottle. The
samples were taken to the γ-counter and measured immediately if possible. The final
activity of Nb-95 and Se-75 in the sorption samples was determined from duplicates.
Tracer standard samples and Milli-Q-water background samples were measured
together with the sorption samples. The volume of the standard and background samples
was equal with the volume of the activity measurement samples. Kd was calculated as
presented in Equation 4. The Kd uncertainties presented in the following Chapters and
Appendices are geometric standard deviations or standard deviations.
3.2 Batch sorption studies
The sorption of radionuclides on different materials is usually examined and estimated

by batch sorption technique (e.g. Aldaba et al. 2010). In this method the solid sample,
e.g. soil or sediment, is suspended to a substantially larger volume of liquid.
Radioactive tracer is added, suspension is equilibrated for the desired time and
radionuclide concentration is measured in the liquid phase after phase separation and
liquid filtering (e.g. Hsu & Chang 1994; Lee et al. 2008; Sheppard et al. 2009b,
2011).The distribution of radionuclide between solid and liquid phases is determined
and the distribution coefficient (Kd) is calculated.
45

The sorption of Cs-134, Cl-36, I-125, Nb-95, Se-75 and Tc-99 was studied on humus
and mineral soil samples in aerobic and/or anaerobic conditions as a function of time.
Soil samples were from the excavator pits OL-KK14, OL-KK15, OL-KK16, OL-KK20
and OL-KK21.
3.2.1 Experiment series programme
Batch sorption tests were done in different phases depending upon the choice of the
material and radionuclide, thus creating an experiment series programme. The
experiments and programme were started with the samples of OL-KK14, OL-KK15 and
OL-KK16. The nuclides Cs-134, I-125 and Tc-99 were examined first. In the second
phase, OL-KK20 aerobic and anaerobic mineral soil samples were used in the studies
for the same nuclides. Thirdly, the sorption of Cl-36 was examined on mineral soil and
humus samples. In the final stage of the experiments Nb-95 and Se-75 were included.
The sorption experiments are still continued and the results will be reported later.
Table 9 presents the studied radionuclides and soil samples in accordance with the
grouping of the sorption experiment series. All the conducted batch series are included.
Table 9. Sorption experiment sequence and the grouping of the materials and
radioactive tracers Cs-134, Cl-36, I-125, Nb-95, Se-75 and Tc-99.
Sampling Nuclide
Sorption experiment series
site Cs-134 Cl-36 I-125 Nb-95 Se-75 Tc-99
OL-KK14 x x x
on dried and fractioned soil
OL-KK15 x x x
samples
OL-KK16 x x x
as a function of time on aerobic OL-KK20 x x x x x x
untreated soil samples OL-KK21 x x
as a function of time on OL-KK20 x x x x x
anaerobic untreated soil
samples OL-KK21 x
on dried and fractioned samples
OL-KK15 x
of humus layer
as a function of time on
untreated soil samples of humus OL-KK21 x x x x x x
layer
irradiated soil samples of OL-KK21 x x x
humus layer
effect of competing cations OL-KK20 x
Table 10 presents a detailed and descriptive summary of the experimental series

programme conducted with the radioactive tracers Cs-134, Cl-36, I-125, Nb-95, Se-75
and Tc-99. Figures, corresponding page numbers and Appendices attributed to a certain
radionuclide and sorption experiment series are given.
46

Table 10. Summary of the sorption experiments conducted with radioactive tracers Cs-134, Cl-36, I-125, Nb-95, Se-75 and Tc-99.
Nuclide Sorption Sampling site Figures Page number Appendix
experiment series (page number)
OL-KK14
samples
OL-KK15 30, 31, 32 52, 53, 54 5.1 (127), 5.2 (128)
OL-KK16
5.3 (129), 5.4 (130; OL-
as a function of time on aerobic OL-KK20
untreated soil samples
33, 34 55, 57 KK20), 5.5 (131; OL-
OL-KK21
KK21)
Cs-134 as a function of time on
anaerobic untreated soil OL-KK20 34, 35 57, 58 5.3 (129), 5.4 (130)
samples
untreated humus samples
OL-KK21 36 59 -
effect of competing cations OL-KK20 37, 38, 39, 40, 41 61, 62, 63, 63, 64 5.6 (132-133)
on untreated soil samples in
aerobic conditions
OL-KK20 - - -
on dried and fractioned humus
samples
OL-KK15 43 67 6.1 (134)
Cl-36
46
OL-KK21 44 68 6.2 (135)
irradiated humus samples
OL-KK21 - - 6.2 (135)
OL-KK14
samples
OL-KK15 7.1 (136), 7.2 (137)
45, 46 71, 72
OL-KK16
as a function of time on aerobic OL-KK20
untreated soil samples
47 74 7.3 (138)
OL-KK21
I-125 as a function of time on
anaerobic untreated soil OL-KK20 - - 7.3 (138)
samples
OL-KK21 48 76 7.4 (139)
OL-KK21 - - 7.4 (139)
- Figure/Appendix not added to the report
47

Table 10. Summary of the sorption experiments conducted with radioactive tracers Cs-134, Cl-36, I-125, Nb-95, Se-75 and Tc-99.
Nuclide Sorption Sampling site Figures Page number Appendix
experiment series (page number)
aerobic untreated soil OL-KK20 50, 51, 52 80, 81, 82 8.1 (140), 8.2 (141)
samples
Nb-95 anaerobic untreated soil OL-KK20 52, 53 82, 83 8.1 (140) , 8.2 (141)
samples
OL-KK21 54 84 8.3 (142)
aerobic untreated soil OL-KK20 56, 57 87, 88 9.1 (143), 9.2 (144)
samples
Se-75 anaerobic untreated soil OL-KK20 58 89 9.1 (143) , 9.2 (144)
samples
OL-KK21 59 90 9.3 (145)
47
OL-KK14
OL-KK15 61 93 10.1 (146)
samples
OL-KK16
aerobic untreated soil OL-KK20 62 94 10.2 (147)
samples
Tc-99 as a function of time on
OL-KK20
anaerobic untreated soil 63 95 10.2 (147)
OL-KK21
samples
OL-KK21 64 96 10.3 (148)
OL-KK21 - - 10.3 (148)
- Figure/Appendix not added to the report
48

3.2.2 Aerobic soil samples
Sorption experiments with radioactive tracers in the aerobic conditions were usually
conducted as follows: 1.00 g of soil sample was weighted into a 50 ml Sorvall®
polypropylene centrifuge tubes. Soil solution simulant (25 ml) and tracer were added
and the tubes were placed onto a reciprocal shaker. After the selected time had elapsed,
ranging from 1 day to several weeks, solid and liquid phases were separated by
centrifugation (Sorvall®, rotor SS-34 or Beckmann Coulter Avanti J-26 XPI, rotor JA-
25.50), and the liquid was further filtered through 0.2 µm syringe filter (Life Sciences,
Supor® Membrane) into a 50 ml PE-centrifuge tube (VWR). Equilibrium pH was
measured from the filtered solutions. Samples for the activity measurement were done
as described in Section 3.1.4.
Batch tests to study the effects of competing cations on the sorption of caesium were
done similarly, but the soil solution simulant was replaced with electrolyte solution.
The equilibrium times varied depending on the radionuclide and sampling site. Table 11
presents the equilibrium times used in the sorption experiments of radionuclides.
Table 11. The equilibrium times used for the sorption experiments of Cs-134, Cl-36, I-
125, Nb-95, Se-75 and Tc-99 on soil samples of OL-KK14, OL-KK15, OL-KK16, OL-
KK20 and OL-KK21.
Equilibrium time (days)
OL-KK14 OL-KK15 OL-KK16 OL-KK20 OL-KK21

Nuclide
aerobic anaerobic aerobic anaerobic
mineral mineral mineral
humus humus humus mineral mineral humus mineral mineral
soil soil soil
soil soil soil soil
Cs-134 91 21 91 21 135 30 1-245 1-28 7-23 1-112 -
Cl-36 - - 7-93 - - - 7 - 7-365 - -
I-125 92 14 92 14 92 15 7-147 1-21 1-93 7-63 -
Nb-95 - - - - - - 7-63 1-21 1-28 - -
Se-75 - - - - - - 7-63 7-33 1-63 - -
Tc-99 91 14 91 14 91 14 7-217 7-33 7-93 - 32-364
- sorption experiments not done
Typically two or three tracer activity standard samples, i.e. tracer samples containing
the same activity as in the sorption samples but within a known volume (10 ml or 15 ml
for γ-emitters and 8 ml for β--emitters) were done when the radioactive tracer was added
to the sorption samples. Activity standards were used to calculate the fraction of the
radionuclide sorbed on the soil samples, and thus define the Kd value.
3.2.3 Anaerobic soil samples
To study the effect of the redox conditions on the sorption of radionuclides, part of the
sorption tests were carried out in the nitrogen filled glovebox. Oxygen and carbon
dioxide levels in the N2- atmosphere were below 4 and 0.1 ppm throughout the test
series. For many redox sensitive elements, such as technetium and selenium, the change
49

to more reducing conditions typically enhances their sorption (Ashworth & Shaw
2006a; Ashworth et al. 2008; Lieser & Bauscher 1987; Sheppard et al. 1990).
At the beginning of the anaerobic sorption test, a set of 20 ml glass scintillation bottles
or polypropylene centrifuge tubes were weighted. Bottles or tubes were transferred to
the glovebox where approximately one gram of the soil sample was added to the
containers. The containers were brought outside the glovebox, sample mass was
determined and the soil solution simulant and tracer solutions, equilibrated with the
nitrogen atmosphere prior to the addition, were added to the samples in the glovebox.
Samples were left to stand in the glovebox for a chosen time period, during which the
samples were shaken daily to ensure the mixing of the phases. Equilibrium times ranged
from one day to a year, depending on the nuclide. Equilibrium pH and redox potential
were measured, sorption samples in the centrifuge tubes were centrifuged and the liquid
phase was filtered. For the samples in the glass bottles, the liquid phase was transferred
into a 50 ml PE-centrifuge tube after the pH and Eh measurement and the fine
suspended solid material was let to settle down overnight before filtration. Samples for
the tracer final activity measurement were done in the glovebox as described in Section
3.1.4.
Figure 29. A picture of AtmosBagTM containing soil filled steel tubes and sorption
samples (Photo by Sinikka Virtanen/HYRL).
The sorption experiments for Tc-99 on the anaerobic OL-KK21 mineral soil samples
were done similarly, but in the field conditions using AtmosBagTM. 20 ml of soil
solution simulant was added to weighted glass scintillation bottles in the glovebox, and
the bottles were weighted again. Tc-99 tracer was equilibrated with the nitrogen
atmosphere in the glovebox prior to the addition into the water/soil mixture. The
equipment needed in the preparation of the anaerobic sorption samples were packed in a
plastic box, which was transferred into AtmosBagTM. In the field, freshly taken
anaerobic soil samples were transported into AtmosBagTM and the bag was filled with
nitrogen gas (Figure 29). Soil samples were added to the bottles until the liquid surface
was on the desired level. Tc-99 tracer was added and Tc-99 activity standard samples
were done simultaneously. Bottles were closed as tightly as possible and transported to
50

the Laboratory of Radiochemistry in the nitrogen gas filled AtmosBagTM. At the

laboratory, bottles were weighted to determine the soil sample mass. After weighting
the samples were transferred into the glovebox. The rest of the treatment was done as
described above for other samples.
3.2.4 Untreated humus samples
To study if sample drying has an effect on the sorption of radionuclides on humus, an

additional test series was done with untreated humus samples of OL-KK21. Tests were
done accordingly: 25 ml of soil solution simulant was added into 50 ml polypropylene
centrifuge tubes and the tubes were weighted. Humus was added from two to four
grams, so that the liquid surface reached the desired level. The tubes were weighted
again to define the exact sample mass. After tracer addition the tubes were placed on a
reciprocal shaker, equilibrated a chosen time and centrifuged. The liquid phase was
filtered through 0.2 µm syringe filter and the equilibrium pH and tracer activity were
measured.
3.2.5 Irradiated humus samples
Microbial activity has documented to have a great impact on the sorption of elements
(Bunzl & Schimmack 1988; Février et al. 2007). By reducing the microbial activity in
the samples, the sorption of radionuclides may be altered drastically. Therefore a
complementary sorption series was carried out with γ-irradiated, sterile humus samples.
In addition to the microbe population size and their activity, irradiation may cause
changes in the physical properties of the samples, such as structure, particle size or
solubility.
The γ-irradiated sterilized humus samples were done by weighting 2-3 grams of
untreated humus of OL-KK21 into 50 ml polypropylene centrifuge tubes. 25 ml of soil
solution simulant filtered through 0.25 µm filter (PES, Nalgene) was added, and the
tubes were placed in the vicinity of Co-60 source to receive 20 kGy radiation dose.
After irradiation, the tubes were transferred into the glovebox where the radiotracer was
added. The centrifuge tubes were brought outside and placed on a reciprocal shaker,
equilibrated a chosen period and centrifuged. The liquid phase was filtered through 0.2
µm syringe filter and the equilibrium pH and tracer activity were measured.

51

4 RESULTS
The results of the Kd values of Cs-134, Cl-36, I-125, Nb-95, Se-75 and Tc-99 in humus
and mineral soil layers of the deep soil pits OL-KK14, OL-KK15, OL-KK16, OL-KK20
and OL-KK21 at the Olkiluoto Island are presented in the following Chapters. The Kd
values are compared with the Kd values reported in the literature.
4.1 Kd values for caesium
Caesium has only one oxidation state of +I. It does not hydrolyze nor form complexes
in solutions, and occurs solely as hydrated Cs+ ion. Its sorption on mineral surface
hydroxyl groups and functional groups of organic matter takes place via an ion
exchange mechanism, even though the uptake is not efficient because of the large size
and low charge of Cs+ ions. Clay and mica minerals sorb caesium ions very effienctly
on their interlamellar ion exchange sites. Concentrations of caesium in natural waters
are typically very low.
4.1.1 Dried and fractioned soil samples of OL-KK14, OL-KK15 and OL-KK16
The sorption of caesium on dried and fractioned soil samples of different soil layers of
the deep excavator pits OL-KK14, OL-KK15 and OL-KK16 is presented in Figure 30
and Appendix 5. Humus tends to retain caesium poorly compared with the mineral soil
layers MS1-MS5, even though there are differences between the pits and the soil layers
arising from the variance in the CEC and the clay fraction content. The Kd values for the
humus layers of soil pits OL-KK14, OL-KK15 and OL-KK16 were 11 759 ml/g, 198
ml/g and 964 ml/g, respectively. The great variability in the Kd values is due to the
variation in the organic matter (OM) and dry matter contents, and especially in the
mineralogy of the dry matter. The organic matter content was the highest for the soil pit
OL-KK15 (62.6 %) and lowest for OL-KK16 (54.2 %), whereas the highest and lowest
dry matter contents were in OL-KK14 (48.0 %) and OL-KK16 (26.5 %), respectively
(Lusa et al. 2009). High OM content decreases the sorption of caesium, whereas an
increase in the dry matter content has a positive effect on the sorption because caesium
is mainly retained by the soil mineral matter (e.g. Absalom et al. 1995; Cremers et al.
1988; Dyer & Cho 1999; Giannakopoulou et al. 2007; Shenbar & Eriksson 1993).
The sorption mechanism of caesium on organic matter is ion exchange, and the
concentration of other cations, especially divalent and trivalent cations in the solution
restrains the sorption of caesium due the competition of the sorption sites (Bondar &
Zabrodskii 2001; Dumat et al. 1997; Dunigan & Francis 1972; Rigol et al. 2002;
Staunton & Levacic 1999). The large variability in the Kd values cannot be, however,
explained by the differences in the OM and dry matter contents. The most possible
reason is the contents of the clay and mica minerals in the humus layers. Even small
amounts of highly caesium-selective mica and clay minerals among the organic matter
control the level of the sorption. Mineralogical composition of the mineral matter in the
humus layers was not determined and therefore no direct evidence to this is available.
52

OL-KK14
OL-KK15
humus OL-KK16
MS1
MS2
Soil layer
MS3
MS4
MS5
100 1000 10000 100000

Kd (ml/g)
Figure 30. Kd values of Cs-134 for the soil layers of OL-KK14, OL-KK15 and OL-
KK16. The Kd values for each sample depth was calculated as a weighted average of
the Kd values determined for the grain size fractions of >0.063 mm, 0.063-0.125 mm,
0.125-0.25 mm, 0.25-0.50 mm, 0.50-1.0 mm and 1.0-2.0 mm.
A major fraction of Cs+ is sorbed in the mineral soil layers compared with the humus
layer, excluding OL-KK14 (Figure 30). In the mineral soil layers of OL-KK14 and OL-
KK15 the Kd values decrease with increasing soil depth and decreasing clay fraction
content. The lowest Kd values and clay fraction contents in the mineral soil layers were
in the topmost layer MS1. In MS2 soil layers the Kd values were the highest, and so was
the amount of clay fractions. The Kd values for MS1 and MS2 soil layers were 3 041
ml/g and 32 787 ml/g for OL-KK14, and 982 ml/g and 18 949 ml/g for OL-KK15. Kd
values for the other mineral soil layers vary between these ranges. The result is quite
expected, because topsoil layers usually show lower sorption of caesium compared with
the subsoil layers. This is due to the increased weathering and the action of soil forming
processes influencing the surficial parts of soils. Chemical weathering takes place as a
counteract for the soil acidifying caused by the action of the acid load produced by the
natural organic acids liberated in the decomposition of organic matter and carbonic acid,
nitric acid and sulphuric acid originating from the atmosphere and precipitation. As a
consequence the amount of more easily weathered minerals (e.g. olivine and Ca-rich
plagioclase) decrease and the amount of resistant minerals (e.g. quartz and potassium
feldspar) with relatively low sorption capacities increase (Birkeland 1984; Campbell &
Davies 1995; Kónya et al. 2005; Mollah & Ullah 1998; Torstenfelt et al. 1982).
In the soil pit OL-KK16, the highest and lowest Kd values were in the soil layers MS1
(11 288 ml/g) and MS4 (3 157 ml/g). In OL-KK16, the clay fraction content increased
as a function of depth, but the Kd values decreased. Equilibrium pH increased with
depth in all the soil pits, being the lowest in the humus layer (4.5-5.6) and highest in the
bottom mineral soil layers (5.2-8.6). In the mineral soil the most important factors
53

governing the sorption of caesium are the clay mineral content, the nature of the present
clay minerals (expanding or non-expanding, CEC) and the amount of clay sized fraction
(Absalom et al. 1995, Cremers et al. 1988, Giannakopoulou et al. 2007, Shenbar &
Eriksson 1993).
Altogether a general trend to the soil pits OL-KK14, OL-KK15 and OL-KK16 is that
the Kd of caesium has a maximum, on average 20 000 ml/g, at the depth of about 60 cm
and it systematically decreases towards lower depths, being almost an order of
magnitude lower in the deepest sampling depths. Also, at about 30 cm the Kd is
considerably lower than at 60 cm. The reason for this behaviour is the most possibly the
varying clay contents of the layers presented in Figure 31, which shows the correlation
between the Kd values and the clay fraction (< 0.002 mm) content.
25000
20000
Kd (ml/g)
15000
y = 1872,2x + 62,373
R² = 0,7845
10000
5000
0
0 2 4 6 8 10 12
Clay fraction content (%)
Figure 31. The correlation between Cs-134 Kd values and the clay fraction content of
the soil samples.
References concerning the determination of caesium Kd values for soil samples taken at
different sampling depths as done as extensively as in this study were limited in the
literature. For example, Gillham et al. (1990) defined that Cs Kd decreased from 26 000
ml/g to 6 300 ml/g as sample depth increased from 0.9 m to 6.0 m. For another
Canadian soil samples, the decrease was from 7 000 ml/g in sample depth 1.0 m to
4 100 ml/g for sampling depths 4.0 m and 10.0 m. The nature of the samples was not
described in detail. Compared with these values, the experimental values of the studied
soil samples are in a good agreement. The overall average Kd values for the soil pits
OL-KK14, OL-KK15 and OL-KK16 were 13 150 ml/g, 6 054 ml/g and 6 239 ml/g,
respectively. The overall Kd values were calculated by taking an average of the
individual Kd values of the soil layers of each soil pit. The calculation of the Kd values
of the soil layers is described in the caption of Figure 30.
In Figure 32 and Appendix 5 are presented the Kd values of Cs-134 on the dried and
fractioned soil samples of different soil layers of the excavator pit OL-KK15 as a
function of the grain size. Even though the retention typically increases with decreasing
particle size (Baeza et al. 1995; Giannakopoulou et al. 2007; Hsu & Chang 1995; Kamel
& Navratil 2002; Li et al. 2004; Zygmunt et al. 1998), the effect was not so evident to
OL-KK15 samples. Typically the increase in the sorption with decreasing grain size is
54

related to the surface sorption site density of the material; the majority of the sorption
sites are situated on the particle surfaces, and smaller particles have larger surface-area-
to-volume ratio thus increasing their reactivity (Baeza et al. 1995). The retention of
caesium on mineral soil particles increase in the order of clay (<2 µm) ~ very fine silt
(2-5µm) > fine silt (5-10 µm) > coarse silt (10-50 µm) (Li et al. 2004).
humus
10000 MS1
MS2
MS3
MS4
MS5
1000
Kd (ml/g)
100
<0.063 0.063-0.125 0.125-0.25 0.25-0.50 0.50-1.0 1.0-2.0

Grain size (mm)

Figure 32. Kd values of Cs-134 for OL-KK15 sample layers as a function of the grain
size.
For the mineral soil layers MS1, MS3 and MS4 the highest Kd values were for the
smallest grain size <0.063 mm, and the Kd values decreased with increasing particle size
or were rather constant. For MS5, the Kd values decreased from the grain size <0.063
mm to 0.25-0.50 mm and increased again towards larger grain sizes. In the soil layers
MS1, MS3 and MS4 changes in the Kd values followed the changes in the cation
exchange capacity (Figure 13). The respective Pearson’s correlations for the soil layers
of MS1, MS3 and MS4 were 0.9978, 0.9759 and 0.9442. However, for the soil layers of
MS2 and MS5 the highest Kd values were in the grain size fractions of 0.25-0.50 mm
(20 457 ml/g) and 1.0-2.0 mm (6 093 ml/g). The correlation between the Kd and the
cation exchange capacity in MS2 and MS5 were smaller: 0.7359 for MS2 and 0.1944
for MS5.
In the case that the sorption of caesium would take place only on the outer surfaces of
the mineral grains, a clear correlation between the Kd and the grain size would have
been noticed. As this is not the case, it is assumed that the mineral matter is porous and
has sorption sites on the outer surfaces and in its internal space. In addition, dry-sieving,
used in the separation of different grain size fractions for another, does not discriminate
between the same sized individual mineral particles and soil aggregates consisting of
smaller particles cemented together by organic matter and/or weakly crystalline
aluminium and iron oxides for instance. Also, it is possible that the surface of the larger
grains is covered by an attached dust layer comprised of smaller particles.
55

4.1.2 Aerobic untreated soil samples of OL-KK20 and OL-KK21
The retention of caesium on the aerobic untreated soil samples of the excavator pits OL-
KK20 and OL-KK21 decreases as a function of soil depth (Figure 33, Appendix 5) from
the topmost sampling depths, 0.7 m (5 456 ml/g) and 0.4 m (7 256 ml/g) to 3.4 m (1 315
ml/g) and 3.6 m (2 742 ml/g). Also, the Kd values for the samples of OL-KK21 were
higher than for OL-KK20. Since sample mineralogy, pH, OM and dry matter contents
were rather similar and the CEC did not correlate with the Kd values, differences may be
partly due to the different grain size distributions (clay fraction contents) of these two
pits. For OL-KK14, OL-KK15 and OL-KK16 the Kd increased with increasing clay
fraction content (Figure 31), and it is possible that a similar trend is true for OL-KK20
and OL-KK21. However, direct evidence to this is not available since the grain size
distribution analysis of the soil samples of OL-KK20 and OL-KK21 was not done.
0,0
0,5
1,0 OL-KK20
OL-KK21
1,5
Soil depth (m)
2,0
2,5
3,0
3,5
4,0
2000 4000 6000 8000 10000
Kd (ml/g)

Figure 33. Kd values of Cs-134 on the aerobic untreated soil samples of the excavator
pits OL-KK20 and OL-KK21. The Kd value for a specific sample depth was calculated
as an average of all the sorption tests done to the sample depth in question.
The retention of caesium on OL-KK20 and OL-KK21 samples increased with
increasing equilibrium time (Appendix 5). This may be explained as an initial fast
sorption on the external surfaces of the particles, which is followed by a slow diffusion
into the aggregate cores (e.g. Wang & Staunton 2010). The increase in the equilibrium
time thus increases the fraction of caesium in fixed, scarcely exchangeable form in soils.
The Kd values determined for the aerobic untreated soil samples of OL-KK20 and OL-
KK21 were smaller than for dried and fractioned samples of OL-KK14, OL-KK15 and
OL-KK16 at approximately the same depths. For example, Kd for OL-KK14 MS3 layer
at the depth of 0.6-1.05 m was 13 970 ml/g, whereas the respective value for OL-KK20
at sample depth 0.7 m was about 5 460 ml/g. Correspondingly, Kd for OL-KK21 at
sample depth 1.75 m was 3 670 ml/g, whereas for MS4 (1.05-2.4 m) layer of OL-KK14
56

the respective value was 4 190 ml/g. The average Kd values for the soil pits of OL-
KK20 and OL-KK21 were 2 606 ml/g and 4 158 ml/g, while the respective values for
OL-KK14, OL-KK15 and OL-KK16 were 13 150 ml/g, 6 054 ml/g and 6 239 ml/g.
Mineralogy, CEC and grain size distribution are probably important factors explaining
the differences when evaluating the Kd values.
Compared with the literature Kd values for mineral soils including the typical Finnish
soil type till, the results of this study are in a good agreement. Generally, the Kd values
for caesium on soils range from 31 ml/g to 26 000 ml/g (Absalom et al. 1995; Beneš et
al. 1994; Bunzl & Schimmack 1988; Cremers et al. 1988; Gillham et al. 1980; Leqoux
et al. 1992; Mollah & Ullah 1998). For (USDA) soil texture types clay, loam and sand,
the Kd values decreased from 5 500 ml/g to 3 500 ml/g and to 530 ml/g, respectively
(Vidal et al. 2009).
The sorption of caesium on minerals and soils could be affected by pH via the
protonation and deprotonation degree of surface functional groups (Baeza et al. 1995;
Fujikawa & Fukui 1997; Giannakopoulou et al. 2007; Kim et al. 1996; Torstenfelt et al.
1982). As the pH rises, the proportion of negatively charged, deprotonated surface
functional groups acting as cation exchange sites increases. This leads to a higher
negative surface charge, which attracts cations from the solution to balance the charge
for zero (Avery 1996, Baeza et al. 1995, Fujikawa & Fukui 1997, Giannakopoulou et al.
2007, Kamel & Navratil 2002, Torstenfelt et al. 1982). Thus, the sorption of caesium
favours elevated pH values.
Figure 34 and Appendix 5 presents the Kd values determined for the soil samples of OL-
KK14, OL-KK15, OL-KK16, OL-KK20 and OL-KK21 as a function of equilibrium pH.
It is evident from Figure 34 that pH does not have a drastic effect on the sorption of
caesium. Instead, relatively high and low Kd values are noticed approximately at the
same pH values; for example in pH 7.7 Kd values were 901 ml/g (low) and 4 900 ml/g
(high). Therefore, it is assumed that the pH has only a minor effect on the sorption of
caesium on mineral soils at the relevant pH range of 5-9, and the differences obtained in
the Kd values are of variation in the mineralogy and grain size distribution. The
equilibrium pH of the anaerobic samples was higher than for the aerobic samples due to
the absence of carbon dioxide in the nitrogen filled glovebox.
57

Aerobic samples
(time 1-7 days)
Aerobic samples
(time 18-245 days)
Anaerobic samples
1000
Kd (ml/g)
100
5,5 6,0 6,5 7,0 7,5 8,0 8,5 9,0 9,5 10,0
Solution equilibrium pH

Figure 34. Kd values of Cs-134 on the aerobic and anaerobic untreated soil samples of
the excavator pit OL-KK20 as a function of equilibrium pH.
4.1.3 Anaerobic untreated soil samples of OL-KK20
The sorption of caesium on the anaerobic untreated soil samples of excavator pit OL-
KK20 is presented in Figure 35 and Appendix 5. The retention of caesium decreases as
a function of soil depth from 3 319 ml/g at the depth of 0.7 m to 649 ml/g at 3.4 m,
which is possibly due to decrease in the clay fraction content and CEC. A similar trend
was also noticed for the aerobic soil samples (Figures 30 and 33). The average Kd for
the untreated and anaerobic samples from mineral soil layers of soil pit OL-KK20 was
1 629 ml/g.
The Kd values for the anaerobic samples of OL-KK20 were typically smaller than those
of the aerobic samples at the same equilibrium time. For example at five days
equilibrium time the Kd values for the sample depth of 3.4 m were 1 100 ml/g and 600
ml/g for the aerobic and anaerobic samples, respectively. The reason for the decrease in
the retention of caesium in the anaerobic conditions is proposed to be the production of
ammonium ions (NH4+) in reductive redox conditions (Wang & Staunton 2010).
Ammonium ions are capable of competing effectively with caesium of the sorption sites
and to release sorbed caesium into solution (see Section 4.1.2). This has also been
verified in the previous studies of Cremers et al. (1988), Comans et al. (1989) and Hird
et al. (1995). In these studies the Kd values for caesium on the anaerobic soil samples
ranged from 10 ml/g to 4 700 ml/g when measured in natural groundwater, and from 1
ml/g to 2 000 ml/g in synthetíc groundwater (Holgersson 2009). The Kd values in this
study are within these large ranges.
As for the aerobic soil samples, the sorption of caesium in the anaerobic conditions
increased as a function of time. The data is presented in Appendix 5. According to
Wang & Staunton (2010), for instance, the reason is a fast initial sorption on the particle
external surfaces and slow diffusion into the aggregate cores.
58

0,5
1,0
1,5
Soil depth (m)

2,0
2,5
3,0
3,5
500 1000 1500 2000 2500 3000 3500

Kd (ml/g)

Figure 35. Kd values of Cs-134 on the anaerobic untreated soil samples of OL-KK20.
The Kd value for a specific sample depth was calculated as an average of all the
sorption tests done to the sample depth in question.
4.1.4 Untreated humus samples of OL-KK21
The sorption of caesium on untreated humus samples of OL-KK21 is presented in

Figure 36 and Table 12. The retention decreases with increasing equilibrium time,
which is opposite to the behaviour of caesium on the mineral soil samples. The Kd
values for the humus samples range from 6 558 ml/g on day seven to 1 822 ml/g on day
28. The sorption on humus on day seven is at the same level as that on the topmost
untreated mineral soil samples of 0.7 m in OL-KK20 (3 983 ml/g), whereas compared
with the sample depth at 0.4 m of OL-KK21 (7 166 ml/g) the sorption is lower. This is
in a good agreement with the previous studies showing that the sorption of caesium on
organic matter is typically smaller than on soils’ mineral components (Dumat et al.
1997; Rigol et al. 2002).
The sorption of caesium on humic acids and humin increases with increasing pH and
decreasing concentration of competing cations (Dunigan & Francis 1972; Helal et al.
1998). Association with humic acids and humin is non-specific and the sorption is
partly or completely reversible (Helal et al. 1998; Hsu & Chang 1994, 1995; Nakamaru
et al. 2007; Lofts et al. 2002; Rigol et al. 2002). Micro-organisms contribute to the
retention of caesium in organic soils (Parekh et al. 2008, Sanchez et al. 2000), and the
retention of caesium is stronger in biotic environments than in abiotic (Tamponnet et al.
2008). Micro-organisms may increase the retention of caesium on soils by increasing
the surface area of organic matter and by inducing more sorption sites, removing
competing cations from the solution or by biosorption and bioaccumulation through
active K+ transport system (Kakiuchi et al. 2002; Tamponnet et al. 2008).
Based on the results of the sorption experiments, it is possible that soil micro-organisms
are mainly responsible for the sorption of caesium on OL-KK21 humus samples. The
decrease in the sorption over time might be caused by the diminishing of micro-
59

organism population as oxygen and probably nutrient level decreased. Another reason
may be the formation of anaerobic conditions and the production of ammonium ions
(NH4+) leading to enhanced competition of the sorption sites.
7000
6000
5000
Kd (ml/g)
4000
3000
2000
1000
5 10 15 20 25
Time (days)

Figure 36. Kd values of Cs-134 on the aerobic untreated humus samples of OL-KK21 as
a function of time.
According to Bunzl & Schimmack (1988), Holgersson (2009) and Sheppard et al.
(2009b), the Kd values determined for peat range from 10 ml/g to 6 000 ml/g. The
respective value for organic matter is approximately 270 ml/g (Vidal et al. 2009). When
comparing the literature Kd values with the determined values for the untreated humus
samples, they are within the range.
Table 12. Kd values, standard deviations and equilibrium pH values of Cs-134 on

humus samples of OL-KK21.
Standard
Time (days) Kd (ml/g) pH
deviation (ml/g)
7 6 558 724 6.91
14 3 465 2 324 6.69
23 1 822 187 7.42
4.1.5 Effect of competing cations on the sorption of caesium
The sorption of caesium is restrained in high salinity solutions due to enhanced

competition of the sorption sites with the other dissolved cations, whereas in the
solutions of lower ionic strength the competition is weaker (Fujikawa & Fukui 1997;
Hsu et al. 2002; Hurel et al. 2002; Kamel & Navratil 2002; Lee et al. 2008; Lieser &
Steinkopff 1989a; Torstenfelt et al. 1982; Yllera de Llano 1998). The ability of
60

dissolved cations to inhibit the sorption of caesium on soil decreases in the order
Cs+>NH4+>K+>Na+>Ca2+>Mg2+ (Kamel & Navratil 2002; Shenbar & Eriksson 1993).
Table 13 presents the effect of caesium, ammonium and potassium on radiocaesium
sorption on Swedish sand, loamy sand, clay loam and clay soils. Stable caesium has a
greater effect on the sorption of radiocaesium compared with potassium or ammonium.
Table 13. The effect of stable caesium, ammonium and potassium on the sorption of
radiocaesium on different soil types (Shenbar & Eriksson 1993). The initial activity of
the Cs+-134 tracer was 5 kBq.
Kd (ml/g) Kd (ml/g)
Kd (ml/g) Kd (ml/g) Kd (ml/g)
0.153 0.767
Soil type Kd (ml/g) 0.03 mmol 100 mmol 100 mmol
mmol mmol
Cs+/l NH4+/l K+/l
Cs+/l Cs+/l
Sand 1 961 96 45 19 15 94
Loamy
3 512 24 7 4 10 36
sand
Clay loam 4 081 58 18 7 14 99
Clay 6 189 1 274 338 103 39 125
Figures 37-41 and Appendix 5 present the effect of competing cations on the retention
of Cs-134 on the aerobic soil samples of OL-KK20. Stable Cs+ competes effectively
with radiocaesium of sorption sites and can remove radiocaesium from ion exchange
sites by isotopic exchange (Avery 1996; Beneš et al. 1994; Comans et al. 1991; Cornell
1991; Gillham et al. 1980; Hsu & Chang 1995; Lujanienė et al. 2006; Wang & Staunton
2010). When soil contains relatively high amounts of stable Cs and clay minerals,
radiocaesium is sorbed mainly reversibly via ion exchange on the clay minerals regular
sorption sites, termed as RES (Kamei-Ishikawa et al. 2008; Lujanienė et al. 2006). If
competing stable caesium is not present, radiocaesium may be sorbed irreversibly on
high affinity interlayer sites on the edges (frayed edge sites; FES) (Lujanienė et al.
2006).
According to Figure 37, Appendix 5 and Table 11, relatively low concentrations of
stable caesium in solution have a great impact on the sorption of radiocaesium. In soil
solution simulant with one week equilibration time Kd values ranged from 4 184 ml/g at
the sample depth 0.7 m to 580 ml/g at the sample depth of 3.4 m, the average Kd being
1 827 ml/g. The Kd values for the same sampling depths in 0.01 mM CsCl were 215
ml/g and 49.3 ml/g, whereas in 10 mM CsCl the respective values were only 1.05 ml/g
and 0.92 ml/g. In the caesium solutions and the soil solution simulant the Kd values
decreased as a function of depth. In the analysed samples of soil solution from
Olkiluoto, caesium concentration was 0.03 µM at maximum (Lusa et al. 2009). The
lowest concentration in this experiment series was approximately at the same level, as
the carrier concentration (stable caesium) for Cs-134 in soil water simulant was 0.02
µM. The concentration of stable caesium in 10 µM solution was more than 3400-times
higher compared with the natural level. Thus, it is quite possible that the Kd values for
radiocaesium in Olkiluoto soils are similar to the values determined for Cs-134 in pure
soil water simulant.
61

0,5
1,0
1,5
Soil depth (m)
2,0
2,5 Soil water simulant

0.01 mM CsCl
0.1 mM CsCl
3,0
1 mM CsCl
10 mM CsCl
3,5
0,1 1 10 100 1000
Kd (ml/g)

Figure 37. Kd values of Cs-134 on the soil samples of OL-KK20 in the presence of 0.01
mM, 0.1 mM, 1 mM and 10 mM of stable Cs+ as a competing cation.
Radiocaesium is retained much better than sodium on the soil sorption sites in 0.1 mM
and 1 mM NaCl solutions (Figure 38, Appendix 5). When sodium concentration
increases to 10 mM, the radiocaesium Kd values decrease below the Kd values
determined in the soil solution simulant. The Kd values for sampling depths 0.7 m and
3.4 m in 0.1 mM NaCl were 8 892 ml/g and 1 719 ml/g, which are considerably higher
than the respective values determined in the soil solution simulant (4 184 ml/g and 580
ml/g). The soil solution simulant contained minor concentrations of potassium, which
competes efficiently with caesium of the sorption sites and thus leads to smaller Kd
values. In 1000 mM NaCl the Kd values were 163 ml/g and 55.3 ml/g for sampling
depths 0.7 m and 3.4 m, respectively. The Kd values for Cs-134 decreased to some
extent as a function of depth in NaCl solutions. The maximum sodium concentration in
the analysed samples of Olkiluoto soil solution was approximately 0.70 mM (Lusa et al.
2009). It can be concluded that sodium is not very efficient in the competition of the soil
sorption sites at the low concentrations found in Olkiluoto soils.
62

0,5
1,0
Soil depth (m)

1,5

0.1 mM NaCl
1 mM NaCl
2,5
10 mM NaCl
100 mM NaCl
3,0 1000 mM NaCl
3,5
1 10 100 1000 10000
Kd (ml/g)

mM, 1 mM, 10 mM, 100 mM and 1000 mM of stable Na+ as a competing cation.
K+ and NH4+ ions can compete efficiently with Cs+ ions of the sorption sites situated on
the soil surfaces and clay mineral interspaces due to their chemical similarity and
uniform behaviour (Avery 1996; Brouwer et al. 1983; Comans et al. 1989; Konopleva et
al. 2009; Rajec & Shaw 1994; Rigol et al. 2002; Shenbar & Eriksson 1993). K+ ions
have been found to be the main competitor to Cs+ in soils and NH4+ mainly in anoxic
sediments and soils (Cremers et al. 1988; Comans et al. 1989; Wang & Staunton 2010).
Figures 39 and 40 present the Kd values of Cs-134 on the aerobic soil samples of OL-
KK20 in the presence of the increasing concentrations of potassium (Fig. 39) and
ammonium (Fig. 40). The Kd values, uncertainties and equilibrium pH values are
presented in Appendix 5.
Potassium and ammonium inhibit the sorption of caesium on soil samples much better
than sodium. Lower Kd values than in the soil solution simulant were determined in 0.1
mM solutions. The Kd values for sampling depths 0.7 m and 3.4 m in 0.1 mM KCl were
3 032 ml/g and 521 ml/g, whereas the respective values in 0.1 mM NH4Cl were 1 281
ml/g and 399 ml/g. For both, potassium and ammonium ions, zero Kd values for Cs-134
were obtained partly in 10 mM and completely in 100 mM and 1 000 mM solutions. Cs-
134 Kd values decreased as a function of depth in KCl and NH4Cl solutions. The
maximum potassium concentration in the analysed samples of Olkiluoto soil solution
was approximately 0.42 mM (Lusa et al. 2009). Based on the research carried out,
potassium and ammonium have considerable affinity to the soil sorption sites, and they
compete effectively with caesium; ammonium slightly better than potassium.

63

0,5
1,0
Soil water simulant

1,5
Soil depth (m)
0.1 mM KCl
1 mM KCl
2,0 10 mM KCl
100 mM KCl
1000 mM KCl
2,5
3,0
3,5
100 1000 10000
Kd (ml/g)

mM, 1 mM, 10 mM, 100 mM and 1000 mM of stable K+ as a competing cation. Negative
Kd values are not shown on the logarithmic scale.
0,5
1,0
1,5
Soil depth (m)
2,0
Soil water simulant

2,5 0.1 mM NH4Cl
1 mM NH4Cl
3,0 10 mM NH4Cl
100 mM NH4Cl
1000 mM NH4Cl
3,5
10 100 1000 10000
Kd (ml/g)

mM, 1 mM, 10 mM, 100 mM and 1000 mM of stable NH4+ as a competing cation.
Negative Kd values are not shown on the logarithmic scale.
64

The competitive effect of calcium ions on the sorption of caesium on samples of OL-
KK20 is more comparable to that of sodium than of potassium or ammonium. The Kd
values for sampling depths 0.7 m and 3.4 m in 0.1 mM CaCl2 were 5 371 ml/g and 862
ml/g. In 1000 mM CaCl2 the respective Kd values were 238 ml/g and 61.4 ml/g (Figure
41). The radiocaesium Kd values decreased as a function of depth in CaCl2 solutions.
The maximum calcium concentration in the analysed samples of Olkiluoto soil solution
was approximately 0.62 mM (Lusa et al. 2009). Thus, calcium does not compete
efficiently with radiocaesium of the soil sorption sites at low calcium concentrations
found in Olkiluoto soils.

0.1 mM CaCl2
1 mM CaCl2
1,0
10 mM CaCl2
100 mM CaCl2
1,5
1000 mM CaCl2
Soil depth (m)
2,0
2,5
3,0
3,5
10 100 1000
Kd (ml/g)

mM, 1 mM, 10 mM, 100 mM and 1000 mM of stable Ca2+ as a competing cation.
Based on the results of the competing cations carried out with OL-KK20 mineral soil
samples, the efficiency of dissolved cations to inhibit the sorption of radiocaesium on
soils decreases in the order Cs+ > NH4+ > K+ > Ca2+ > Na+. This order was obtained by
calculating one single Kd value for each cation, which included all the studied solutions
and sample depths. According to Kamel & Navratil (2002) and Shenbar & Eriksson
(1993) the effect of competing cations decreased in the order Cs+ > NH4+ > K+ > Na+ >
Ca2+ > Mg2+.
4.1.6 Recommendations of the Kd values for caesium
Figure 42 presents the Cs-134 Kd values as a function of soil depth on soil samples of
humus and mineral soil layers of the excavator pits OL-KK14, OL-KK15, OL-KK16,
OL-KK20 and OL-KK21. These values were used in the estimation of the
recommended conservative and realistic Kd values for Cs-134 (Table 14). The
conservative Kd value was the smallest value in a given data group, e.g. among the
humus samples, whereas the realistic Kd value was calculated as the geometric mean
(GM) value of the data group. The log-normally distributed log-transformed GM values
65

are typically preferred above arithmetic mean (AM) values in the description of the Kd
data (Vidal et al. 2009). The Kd values determined in the experiment serie ‘Competing
cations’ were omitted in the estimation procedure because these do not describe the
sorption process taking place in the natural conditions. Also, the Kd values determined
for the irradiation sterilized samples were not included in the humus data set because
microbial activity is typically ubiquitous everywhere in soils. The range of determined
Kd values for humus and mineral soil samples in the sorption tests at the specific soil
depths are given in Table 14.
Soil depth:
0 humus
5-30 cm
50
30-100 cm
100-200 cm
>200 cm
100
150
Soil depth (cm)
200
250
300
350
400
100 1000 10000
Kd (ml/g)
Figure 42. Kd values of Cs-134 on the aerobic and anaerobic soil samples of the
excavator pits OL-KK14, OL-KK15, OL-KK16, OL-KK20 and OL-KK21 as a function
of soil depth used in the estimation of the recommended conservative and realistic Kd
values. The Kd values determined in the experiment serie ‘Competing cations’ and
irradiation sterilized humus samples were omitted.
The conservative Kd values of Cs-134 are higher in the mineral soil, 350-863 ml/g,
compared with humus, 109 ml/g. The similar behaviour was also seen for the realistic
Kd values. The conservative and realistic Kd values did not show a systematic
correlation with the soil depth. According to Vidal et al. (2009) the GM Kd value of
caesium increased with the clay content being 5 500 ml/g for clay soil. The lowest value
was in the organic soil, 270 ml/g (Vidal et al. 2009).
66

Table 14. The range of the Kd values determined for Cs-134 in the sorption tests and the
recommended conservative and realistic Kd values.
Soil Conservative
Kd range Realistic Kd
depth Soil type N Kd value
(ml/g) value (ml/g)
(cm) (ml/g)
109 –
humus 36 100 1 000
21 223
863 –
5-30 top mineral soil 24 860 5 200
19 498
intermediate 573 –
30-100 108 570 7 300
mineral soil 40 039
deep mineral 835 –
100-200 103 830 4 000
soil 13 874
deep mineral 350 –
>200 180 350 1 800
soil 25 853
4.2 Kd values for chlorine
Chlorine occurs in solutions as chloride ion Cl-, which is a common anion in soil
solutions regardless of the solution pH or the redox conditions. In the soil solution
simulant used in this study chloride concentration was 0.36 mmol/l. Interaction of Cl-
with mineral surfaces is very weak and in general it is considered as a non-retaining ion.
Possible sorption takes place by the uptake on protonated M-OH2+ groups on the
mineral surfaces, and the sorption reaction is favoured by low pH values. It has been
proposed that chloride can be incorporated into organic substances, i.e. chlorinated
organic compounds are formed.
4.2.1 Aerobic untreated soil samples of OL-KK20
The sorption of Cl-36 on mineral soil samples taken from the depths 0.7 and 3.4 m of
OL-KK20 was remarkably low and the calculated average Kd values (± geometric
standard deviation) were 0.13±0.26 and 0.10±0.13 ml/g, respectively. Thus, within the
uncertainty limits these values are identical. The Kd values for the sample depth 0.7 m
varied between 0.00 and 0.64 ml/g, when the respective variation for the sample depth
3.4 m was 0.00-0.28 ml/g.
The retention of chlorine in the chloride form (Cl-) on mineral soils takes place through
non-specific sorption (i.e. anion exchange) due to electrostatic attraction between
positively charged surfaces and negatively charged chloride ions (Katou et al. 1996,
Viers et al. 2001, Yoshida et al. 1992). Sorption is favoured at low pH values below the
pHpzc (pH point of zero charge) of the material. At these pH values the surface charge of
the soil particles becomes more positive, and a higher proportion of the surface
functional –M-OH groups are protonated into –M-OH2+ form (Viers et al. 2001). In
Finnish mineral soils uptake by anion exchange is practically non-existing due to rather
high soil pH, thus decreasing the sorption of chloride (e.g. Yli-Halla et al. 2000; Viers et
al. 2001). Organic matter is the main sorbent for chlorine (Sheppard et al. 1996, 2006).
67

The Kd values of chloride in mineral soils has been found to be close to 0 ml/g (Baston
et al. 1992; Kashparov et al. 2007; Sheppard, et al. 1993) and experimental results of
OL-KK20 are in a good agreement with these studies. The typical Kd value for Cl-36 on
mineral soil has been in the range of 0-0.63 ml/g (Gil-García et al. 2009; Rumynin et al.
2004; Sheppard et al. 1993). Higher values for indigenous chloride range from 0.036
ml/g to 12 ml/g (Sheppard et al. 2009b).
4.2.2 Dried and fractioned humus samples of OL-KK15
The sorption of Cl-36 on OL-KK15 humus samples dried and sieved into different grain
size fractions increased with the equilibrium time (Figure 43, Appendix 6). After one
week, the Kd was approximately 0 ml/g for all the fractioned samples. In three months
time the Kd ranged from 20 to 61 ml/g. The highest Kd was found for the grain size
<0.063 mm, and the lowest for the grain size 0.063-0.125 mm. In the other grain size
classes there was little or no variation in the Kd value. Change in the sample pH
between one week and three months time was within 0.2 pH units, as the average pH
increased from 4.29 to 4.36.
<0.063
0.063-0.125
Time 0.25 months
0.125-0.25 Time 3 months
Grain size (mm)
0.25-0.5
0.5-1.0
1.0-2.0
2.0-
0 10 20 30 40 50 60
Kd (ml/g)

Figure 43. Kd values of Cl-36 on the dried and fractioned humus samples of OL-KK15.
There is no differences in the sorption behaviour of chlorine on mineral soil and dried
and fractioned organic soil in one week equilibrium time, but after three months the Kd
values for the humus samples are noticeably higher proving the role of organic matter as
the main sorbent for chlorine in soils. This indicates that chlorine is sorbed on humic
substances dissolved from the organic matter during the equilibration time or
chlorination of the solid material took place. In the nature, chloride associates preferably
with low molecular weight humic substances compared with high molecular weight
humic substances (molecular size >0.01 µm), which may be due to the differences in the
functional groups and their amounts (Lee et al. 2001). Also, in soils the chlorination
68

reaction, i.e. the formation of chemical bonds between chlorine and the organic
compounds, favours small fulvic and humic substances (Asplund & Grimwall 1991;
Bastviken et al. 2007), which are often relatively mobile and bioavailable.
However, the results for the dried and fractioned humus samples of OL-KK15 are for
pretreated samples and thus they are not representative to the soil organic matter in the
natural conditions. Typically humus samples can be dried but not sieved into different
grain size fractions, which was done in order to find differences in the sorption
behaviour between the grain size fractions. Thus, the Kd values for humus samples of
OL-KK15 should be handled with a precaution.
Untreated humus samples retain Cl-36 rather poorly (Figure 44, Appendix 6); the Kd
values are in the range of 0.31 and 1.67 ml/g. The highest Kd values was for the humus
sample No. 2, for which the OM content was the highest (14.2 %) and equilibrium pH
the lowest (5.5-6.73) among the studied samples. For the humus samples No. 1 and 3,
the OM content was 11.2 % and 9.6 %, whereas the equilibrium pH values were 6.68-
8.45 and 6.96-7.65, respectively. Longer equilibration decreases the sorption of chlorine
and the Kd values drop within one year. This may be due to a decrease in the microbial
activity of the samples with time.
10
humus 1
humus 2
humus 3
Kd (ml/g)
0 50 100 150 200 250 300 350 400

Time (days)
Figure 44. Kd values of Cl-36 on the aerobic untreated humus samples 1, 2 and 3 of
OL-KK21 as a function of time.
The test series was conducted with the samples of humus layers of the excavator pits
OL-KK15 and OL-KK21 located in the vicinity of the harbour road (OL-KK15) in the
northern part of the island, and the main road (OL-KK21) in the southeastern corner of
the island (Figure 2). The different locations may induce differences in the chemical and
physical composition of the soils by variation e.g. in the vegetation cover. Compared
with the dried and fractioned humus samples of OL-KK15, the sorption of chlorine on
the untreated humus was very low, only slightly higher than on the mineral soil
69

samples. Reasons in the sorption difference of chloride between OL-KK15 and OL-
KK21 samples may be smaller OM content, 62.6% in OL-KK15 compared with 9.6-
14.2% in OL-KK21, and higher equilibrium pH (average 4.4 versus 6.0-7.5). Untreated
soil samples can be seen as more representative of the organic matter found in the field
conditions, and thus Kd values determined for OL-KK21 samples can be considered as
more relevant.
The results indicate that the organic matter is only slightly more efficient sorbent for
chlorine than mineral soil, even though it can not retain Cl-36 or reduce its migration
significantly.
4.2.4 Irradiated humus samples of OL-KK21
Micro-organisms control the concentration of inorganic chloride (Clinorg) in soil solution

(Bastviken et al. 2007) and they have an active role in the production of organochloride
compounds in the nature (e.g. Asplund & Grimwall 1991, Bastviken et al. 2007; Hjelm
et al. 1995; Keppler et al. 2000; Rohlenova et al. 2009; Öberg & Grøn 1998). The
organochloride compounds are present everywhere in soil, organic matter and surface
waters, and the amount of organic chloride (Clorg) is higher than the amount of inorganic
chloride (Clinorg) in soils (Asplund & Grimwall 1991; Rohlenová et al. 2009; Öberg &
Grøn 1998). In spite of the multiple roles of the micro-organisms in the cycle of
chlorine in soils, in the experiments with the humus samples of OL-KK21, the role of
micro-organisms seems to be minor. The determined Kd values are in the same range for
the untreated and irradiation sterilized samples, 0.31-1.67 ml/g and 0.80-1.55 ml/g,
respectively. The Kd values, their uncertainties and equilibrium pH values are given in
Appendix 6 for irradiation sterilized humus samples 1, 2 and 3 of OL-KK21.
4.2.5 Recommendations of the Kd values for chlorine
The data set of the determined Kd values in the sorption tests and used in the calculation
of the conservative and realistic Kd values of chlorine consisted of the untreated humus
samples of OL-KK21 and mineral soil samples of OL-KK20. The humus samples of
OL-KK15 were omitted due to the pretreatment (drying and sieving) and relatively high
Kd values compared with the fresh humus samples of OL-KK21. Also, the Kd values for
the irradiation sterilized samples were excluded because microbial activity is typically
ubiquitous in soils. The range of the determined Kd values for humus and mineral soil
samples in the sorption tests are given in Table 15, which also includes the
recommended conservative and realistic Kd values for chlorine.
The conservative and realistic Kd values of chlorine are higher on the humus compared
with the mineral soil, e.g. the realistic values being 0.77 ml/g and 0.13 ml/g,
respectively. The desorption GM Kd value for indigenous chlorine on organic soil has
been estimated to be 150 ml/g, whereas the respective value for mineral soil was 1.4
ml/g (Sheppard et al. 2009b). The values determined in this study are far lower, which
may arise from the differences in the way of determination; Sheppard et al. (2009b)
estimated the Kd values based on the desorption of indigenous chlorine, whereas the Kd
values gained in this study are established on the radiotracer sorption. Sheppard et al.
(2009b) stated that the desorption GM Kd values would be more presentative because of
the formation of less soluble forms of organochlorine by the action of soil microbes or
plants, for instance.
70

Table 15. The range of the Kd values determined for Cl-36 in the sorption tests and the
Soil
Kd range Conservative Realistic Kd
depth Soil type N
(ml/g) Kd value (ml/g) value (ml/g)
(cm)
0.0 - 1.94
humus 39 0.20 0.77**
(0-61)*
top mineral
5- >200
soil – deep 0.0 - 0.64 8 0.0 0.13
cm
mineral soil
* range if OL-KK15 samples are included
** if OL-KK15 organic humus soil samples are taken into consideration when GM value for humus is
calculated, the corresponding value would be 1.5 ml/g (n=59).
4.3 Kd values for iodine
Iodine is a redox-sensitive element and is met in oxidation states –I, O, +I and +V in the
natural conditions. The typical form of iodine in reducing conditions is iodide ion (I-,
oxidation state –I) while oxidising conditions and alkaline solutions favour iodate ions
(IO3-, oxidation state +V). In turn, molecular iodine (I2) is favoured by low pH and high
redox potential. It is slightly soluble in water; 2.3 mmol/l at 20 oC. Sorption of iodide on
minerals is very weak and takes place in the similar manner to chloride, by uptake to
protonated M-O-H2+ groups on minerals surfaces. The sorption of iodate is in general
higher than that of iodide and takes place by ligand exchange mechanism. Sorption of
both, iodide and iodate, increases with decreasing pH. As in the case of chlorine,
organic matter retains iodine better than mineral soil and formation of iodinated organic
compounds is possible.
The sorption of iodine on the dried and fractioned soil samples of the different layers of
excavator pits OL-KK14, OL-KK15 and OL-KK16 decrease with increasing sample
depth (Figure 45, Appendix 7) corresponding to a decrease in the organic matter content
and increase in the pH. In all the studied soil pits, the Kd values are the highest in
humus, ranging from 77.6 ml/g for OL-KK16 to 2700 ml/g for OL-KK15. In OL-KK14,
OL-KK15 and OL-KK16 the Kd values for MS1 were 54.9 ml/g, 2.14 ml/g and 18.3
ml/g, respectively. These values are higher than determined for the underlying soil
layers, where the Kd values typically ranged between 0 ml/g and 2.72 ml/g. Grain size
did not have a marked effect on the retention of iodine on soil (see Appendix 7) even
though previously sorption has found to increase with decreasing particle size (Fukui et
al. 1996; Yuita & Kihou 2005).
71

humus
MS1 OL-KK14
OL-KK15
MS2 OL-KK16
Soil layer
MS3
MS4
MS5
0,01 0,1 1 10 100 1000

Kd (ml/g)

Figure 45. Kd values of I-125 for the soil layers of OL-KK14, OL-KK15 and OL-KK16.
The Kd values for each sample depth was calculated as a weighted average of the Kd
values determined for the grain size fractions of >0.063 mm, 0.063-0.125 mm, 0.125-
0.25 mm, 0.25-0.50 mm, 0.50-1.0 mm and 1.0-2.0 mm.
The results of this study give support to the previous findings of Whitehead (1973,
1978) of iodine being mostly retained by the soil organic matter. A high positive
correlation was found between the iodine Kd values and the soil organic matter content,
as the Pearson correlation coefficient ranged from 0.98001 to 0.9999. The equilibrium
pH had also a visible effect on the sorption of iodine, the Kd values decreasing with
increasing pH. The Pearson correlation coefficient for the Kd value and equilibrium pH
ranged from -0.7804 to -0.9139. The influence of the rising pH has been verified for
organic and mineral soils previously, and has been explained as a change in the surface
charge and the protonation degree of the functional groups (Fukui et al. 1996; Kaplan
2003; Muramatsu et al. 1990; Nishimaki et al. 1994; Yoshida et al 1992; Um et al.
2004; Viers et al. 2001). When soil pH is approximately 3, the sorption is at its
maximum because of the electrostatic attraction between negatively charged iodide (I-)
ions and positively charged soil sorption sites (Ashworth et al. 2003; Evans & Hammad
1995; Fukui et al. 1996). The decrease in the retention is quite abrupt when the pHpzc
(pH point of zero charge) of the soil or mineral is approached (Kaplan 2003). When the
pH value rises above the pHpzc, the sorption reaches steady state being in practise non-
existing. The sorption mechanism of iodide on soil mineral constituents is typically ion
exchange (Lieser & Steinkopff 1989b).
The protonation degree of the surface sorption sites is affected by the pH, but also
conversions in the speciation of iodine can be seen; for example in the very acidic pH
value of 3, 3 % of iodide (I-) was converted into iodate (IO3-) and 60 % to molecular
iodine (I2) (Fukui et al. 1996). The conversion stage to molecular iodine decreased as
pH increased, whereas the conversion to iodate remained within 3-5 % regardless of the
pH. Molecular iodine can remain in the liquid phase.
72

In literature only a few references concerning the determination of iodine Kd values for
soil samples taken at different sampling depths were found. For example, geometric
mean Kd values for soil samples with differing OM contents varied from 2.3 ml/g to 34
ml/g as the OM content increased from 2 % to 10 % (Vidal et al. 2009). In mineral soils
Kd values ranged from 0.0041 ml/g to 73 ml/g (Bors et al. 1991; Holgersson 2009;
Sheppard et al. 2009b; Vidal et al. 2009). Compared with the literature, the
experimental Kd values in this study are in a good agreement for the mineral soil
samples. The values for the humus samples are considerably higher than previously
obtained. Furthermore, it should be taken into consideration that the samples used in
this study were dried and fractioned and the Kd values for the soil layers were calculated
as a weighted average of the Kd values of the studied grain sizes (>0.063 mm, 0.063-
0.125 mm, 0.125-0.25 mm, 0.25-0.50 mm, 0.50-1.0 mm and 1.0-2.0 mm). The overall
average Kd values for the soil pits of OL-KK14, OL-KK15 and OL-KK16 were 132
ml/g, 445 ml/g and 21.5 ml/g, respectively.
Sorption of iodine on the humus layers of OL-KK14, OL-KK15 and OL-KK16 as a
function of equilibrium pH is presented in Figure 46. Three separate groups are
distinguished on the basis of the equilibrium pH, and each group correspond to a certain
soil pit. The highest Kd values were seen for the OL-KK15 samples, which had the
lowest equilibrium pH values (4.4-4.5). The Kd values ranged from 1 867 ml/g to 3 800
ml/g. In OL-KK14 pH and Kd values ranged from 4.7 to 4.8 and from 359 ml/g to 1 242
ml/g, respectively. The lowest Kd values were measured for OL-KK16 humus samples,
10.1-163 ml/g, where also the pH values were the highest (5.4-5.6). The average Kd
values for the humus layers were 604 ml/g, 2 670 ml/g and 77.6 ml/g in OL-KK14, OL-
KK15 and OL-KK16, respectively. The average pH values were 4.7, 4.4 and 5.5. The
equilibrium pH seems to affect the sorption of iodine on humus to some extent as
Pearson correlation between pH and Kd was -0.7422. Sorption of iodine does not show
clear dependence on the grain size distribution. The Kd values, uncertainties and
equilibrium pH values are given in Appendix 7.
OL-KK14 humus
OL-KK15 humus
1000 OL-KK16 humus
Kd (ml/g)
100
10
4,4 4,5 4,6 4,7 4,8 4,9 5,0 5,1 5,2 5,3 5,4 5,5 5,6 5,7

Figure 46. Kd values of I-125 for the humus samples of the excavator pits OL-KK14,
OL-KK15 and OL-KK16 as a function of equilibrium pH.
73

4.3.2 Aerobic untreated soil samples of OL-KK20 and OL-KK21
Sorption of iodine on untreated aerobic mineral soil samples of OL-KK21 decrease with
depth from 136 ml/g for the topmost sample at the depth of 0.4 m to 5.89 ml/g in the
second down most sample at the depth of 2.95 m (Figure 47, Appendix 7). The Kd
values for the samples taken of OL-KK20 show no clear dependence on depth; the
range is from 26.4 ml/g at 2.05 m to 14.2 ml/g at 3.4 m. The Kd values determined for
the OL-KK20 samples were higher than for the samples of OL-KK21, excluding the
sample depth 0.4 m. The higher Kd values for OL-KK20 can possibly be explained with
a higher organic matter content. Equilibrium pH was about the same for the samples of
both soil pits and increased slightly with increasing sample depth. The average Kd
values for OL-KK20 and OL-KK21 were 20.8 ml/g and 31.5 ml/g, respectively.
Soil micro-organisms affect the sorption of iodine. According to Evans & Hammad
(1995), the role of micro-organisms on the sorption of iodine is dual; they increase the
sorption and may decrease it by altering the oxidation states of iodine. Iodate is possibly
retained better on soil constituents compared to iodide (Ashworth & Shaw 2006a;
Ashworth & Shaw 2006b; Fukui et al. 1996; Gil-García et al. 2009), as the reduction of
iodate to iodide as a reason for the difference was ruled out by experiments with iodine
added in the iodide (I-) form. Furthermore, isotopic exchange between stable and
radioactive iodine in soils may take place and have a slight effect on the sorption of
iodine on mineral soil (Bors et al. 1991, Muramatsu et al. 1990, Sheppard et al. 1995).
The Kd values determined for the untreated soil samples are somewhat higher than the
values for the dried and fractioned samples. The average Kd values for the dried and
fractioned mineral soil samples of the layers MS1-MS5 of OL-KK14, OL-KK15 and
OL-KK16 were 14.2 ml/g, 0.57 ml/g and 7.45 ml/g, respectively. The corresponding
values for the untreated samples of OL-KK20 and OL-KK21 were 20.8 ml/g and 31.5
ml/g. The lower Kd values for the samples of OL-KK14, OL-KK15 and OL-KK16
might be caused by a decrease in the population of micro-organisms during sample
pretreatment. For example, Muramatsu et al. (1990) found that sample heating decreases
the sorption of iodine. The organic matter content and equilibrium pH fell in the same
range for all the studied soil samples and thus do not explain the observed behaviour.
The Kd values determined for the untreated aerobic soil samples were in the range of
0.0041-73 ml/g reported by Bors et al. (1991), Holgersson (2009), Sheppard et al.
(2009b) and Vidal et al. (2009).
74

0,0
OL-KK20
OL-KK21
0,5
1,0
Soil depth (m)
1,5
2,0
2,5
3,0
3,5
4,0
1 10 100
Kd (ml/g)

Figure 47. Kd values of I-125 on the aerobic untreated soil samples of the excavator
pits OL-KK20 and OL-KK21. Kd values are calculated as an average of all the sorption
test done to a specific sample depth.
The Kd values determined for dried and fractioned soil samples are not recommended to
be used in the migration modelling of iodine because they may not represent the natural
conditions. It is possible that the drying and fractioning of the samples have induced
changes in the solid phase. Instead, Kd values for the untreated soil samples may give
more relevant results.
The retention of iodine on the anaerobic untreated soil samples of OL-KK20 was
smaller than on the aerobic samples. The average Kd for the aerobic samples of soil pit
OL-KK20 was 0 ml/g, whereas the respective value for the aerobic samples was 20.8
ml/g. In Appendix 7 is presented the Kd values of iodine on the anaerobic soil samples
of OL-KK20.
The reasons for lower sorption on anaerobic soil samples may be the changes in the
speciation of iodine, equilibrium pH and population of micro-organisms. In the
anaerobic, reducing conditions iodine is mainly present as iodide (I-), which is poorly
retained by soil mineral components (Ashworth et al. 2003; Ashworth & Shaw 2006a;
Ashworth & Shaw 2006b; Fukui et al. 1996; Um et al. 2004; Yuita 1992). The effect of
speciation is typically seen in soils at depths below the groundwater surface, as iodine
concentration drastically decreases due to low sorption and relatively high migration
with groundwater (Yuita & Kihou 2005). The equilibrium pH for the anaerobic samples
was 1.5-2.0 pH units higher than for the aerobic samples, ranging from 9.0 to 9.8. The
higher pH values increase the negative surface charge of minerals by increasing the
fraction of deprotonated surface sorption sites (M-O-) thus declining the sorption of
iodide. The population of anaerobic soil micro-organisms decreases more readily at high
75

iodine concentrations (110-980 mg/l) than the population of aerobic micro-organisms

(Sheppard & Hawkins 1995). This may possibly decrease the sorption of iodine in the
anaerobic conditions. Organic matter content was the same for the aerobic and
anaerobic samples of OL-KK20 and OL-KK21.
The Kd values for iodine (I-) determined in the anaerobic conditions by Holgersson
(2009) ranged from -16 ml/g to 19 ml/g. The Kd values for iodine in this study are
within these limits. Since sorption of iodine does not take place in the anaerobic
conditions (see Appendix 7), the Kd value for iodine can be approximated to be zero for
the modelling purposes.
Iodine is typically retained in the soil layer with the highest content of organic matter
and the highest degree of microbial activity (Bostock et al. 2003; Whitehead 1973;
Whitehead 1978). Iodine is sorbed on organic matter on a large pH scale from 2 to 9 and
the sorption is enhanced as the decomposition degree of OM increases (Evans &
Hammad 1995; Whitehead 1974a; Whitehead 1974b). Sorption is proposed to take
place via the amino acid (H2NRCOOH) and phenolic (R-(aromatic ring) -OH)
functional groups (Whitehead 1974b). Sorption mechanism is partly ascribed as a
simple anion exchange reaction, because an increase in the concentration of competing
anions, e.g. Cl-, NO3- and F- decrease the sorption of iodine (Sheppard et al. 1995).
Organic matter can retain considerable amounts of iodine, but the sorption takes place
only on insoluble humic substances, excluding fulvic acids on which the sorption takes
place even in the dissolved form (Bunzl & Schimmack 1988; Fukui et al. 1996;
Muramatsu et al. 1990; Sheppard & Hawkins 1995; Sheppard et al. 1995). On the other
hand, micro-organisms may initiate the incorporation of iodine to organic matter and the
reaction involves extracellular enzymes (Bunzl & Schimmack 1988; Evans & Hammad
1995; Gil-García et al. 2009; Koch-Steindl & Pröhl 2001; Sheppard & Hawkins 1995;
Yoshida et al. 1998).
Figure 48 presents the Kd values of iodine as a function of equilibrium time on humus
samples taken from the vicinity of excavator pit OL-KK21. The retention of iodine
increases for the first five days and decreases afterwards. The highest Kd value of 475
ml/g was found on day five, whereas the lowest Kd 9.59 ml/g was on day 93.
Equilibrium pH ranged from 7.0 to 7.7. The decrease in the sorption of iodine on
untreated humus samples could be explained as a decrease in the population of micro-
organisms with increasing equilibrium time as oxygen and nutrient level drops. Iodine
Kd values on untreated humus samples, uncertainties and equilibrium pH values are
given in Appendix 7.
76

1000
100
Kd (ml/g)
10
1
0 20 40 60 80 100
Time (days)

Figure 48. Kd values of I-125 on the aerobic untreated humus samples of OL-KK21 as a
function of time.
Sorption of iodine on the dried and fractioned humus layer samples of OL-KK14 and
OL-KK15 were considerably higher than on the samples of OL-KK21. The respective
Kd values were 604 ml/g, 2 670 ml/g and 220 ml/g. The difference can be explained by
the variation in the organic matter content and equilibrium pH. The OM content for the
humus samples of OL-KK14, OL-KK15 and OL-KK21 were 58.9 %, 62.6 % and
11.7 %, whereas equilibrium pH values were 4.7, 4.4 and 7.4, respectively.
According to Vidal et al. (2009), the Kd values for iodine on organic soil fall between
2.9-36 ml/g, for peat soils 0-400 ml/g (Bunzl & Schimmack 1988; Sheppard et al.
2009b) and for humic acids 15-40 ml/g (Muramatsu et al. 1990). The Kd values
determined for iodine on humus samples in this study are within the ranges reported in
the literature.
Sterilization of the samples may destroy the living micro-organisms and their by-
products, enzymes (Muramatsu et al. 2004), usually leading to decreased sorption of
iodine (Assemi & Erten 1994; Bird & Schwartz 1996; Devivier et al. 2004; Evans &
Hammad 1995; Gil-García et al. 2009; Muramatsu & Yoshida 1999; Muramatsu et al.
2004; Yoshida et al. 1998). For example, the Kd values for nonsterilized and γ-
irradiation sterilized organic soil samples were 505 ml/g and 150 ml/g, respectively
(Evans & Hammad 1995).
The sorption of iodine on three irradiation sterilized humus samples (1, 2 and 3) taken
from the vicinity of OL-KK21, are smaller at seven day equilibrium time compared
with the nonsterilized humus samples. The Kd values for nonsterilized and sterilized
humus samples were 244 ml/g and 2.51 ml/g, respectively. The increase in the sorption
of iodine on sterilized samples as a function of time was opposite to the trend seen for
the nonsterilized samples; the average Kd value for three humus samples 1, 2 and 3 of
77

OL-KK21 were 6.2 ml/g and 56.6 ml/g for seven days and three month equilibrium
times, whereas the respective Kd values for the nonsterilized samples were 244 ml/g and
9.6 ml/g. Equilibrium pH was approximately 2 units lower for sterilized samples (5.4)
than for nonsterilized samples (7.4).
The reason for the increase in the sorption on sterilized samples with time might be the
increased association of iodine with organic matter. Also, the sorption may take place
on the soil mineral constituents mixed among the humus. The growth of aerobic
microbe population with time is not a realistic explanation, since oxygen level in the
sample tubes would be quite low even though some diffusion through tube walls would
take place.
The Kd values determined in other studies for irradiation sterilized soils range from 14
to 2 000 ml/g (Evans & Hammad 1995; Muramatsu et al. 1990). On average, the Kd
values for the humus samples determined in this study are in the range of 26.9 ml/g to
34.8 ml/g, which is in good agreement with the values reported in the literature.
4.3.6 Recommendations of the Kd values for iodine
Figure 49 presents the I-125 Kd values as a function of soil depth on humus and aerobic
mineral soil samples of OL-KK14, OL-KK15, OL-KK16, OL-KK20 and OL-KK21.
The data set for the humus comprised of the Kd values determined for the samples of
OL-KK14, OL-KK15 and OL-KK16. The Kd values for OL-KK21 samples were
excluded due to the rather high equilibrium pH (8.1) measured in the sorption tests.
Also, the Kd values determined for the irradiation sterilized samples were excluded from
the humus data set because microbial activity is typically ubiquitous everywhere in
soils. The data set for the aerobic mineral soil comprised of the Kd values determined
for the aerobic soil samples of OL-KK14, OL-KK15, OL-KK16, OL-KK20 and OL-
KK21. The estimation of the recommended conservative and realistic Kd values for
iodine in the anaerobic conditions was based on the data set of the Kd values determined
for the anaerobic OL-KK20 mineral soil samples in anaerobic conditions. It is very
likely that there is no differences in the sorption behaviour of iodine in the anaerobic
conditions between different sample pits. The range of the determined Kd values for the
humus and mineral soil samples in the aerobic and anaerobic sorption tests are given in
Table 16, which also presents the recommended conservative and realistic Kd values for
iodine in respective conditions.
The estimated conservative Kd value of iodine was rather high for humus, 10 ml/g,
whereas the corresponding value for aerobic and anaerobic mineral soil was typically 0
ml/g at different depths. The realistic Kd values for aerobic soil somewhat decreased as
a function of depth, being the highest for the humus layer, 460 ml/g, and the lowest at
100-200 cm (3.6 ml/g). The realistic Kd values calculated for the anaerobic soils were
about ten times smaller than the smallest values estimated for the aerobic soils, and the
values decreased with soil depth from 0.5 ml/g at 30-100 cm to 0.2 ml/g at 100-200 cm
and >200 cm.
78

50
Soil depth:
100
humus
5-30 cm
150
Soil depth (cm)
30-100 cm
100-200 cm
200
>200 cm
250
300
350
400
10 100 1000
Kd (ml/g)
Figure 49. Kd values of I-125 on the aerobic soil samples of OL-KK14, OL-KK15, OL-
KK16, OL-KK20 and OL-KK21 as a function of soil depth used in the estimation of the
Vidal et al. (2009) estimated that the GM Kd value of iodine for organic soil was 32
ml/g, whereas the corresponding values for sand, loam and clay were 4.1 ml/g, 8.0 ml/g
and 11 ml/g. Compared with these values, the recommended realistic Kd values for the
aerobic mineral soil are within the same range, whereas the value for humus is
approximately 10-fold.
Table 16. The range of the Kd values determined for I-125 in the sorption tests and
Aerobic soil
Kd range Conservative
Soil depth Realistic Kd
Soil type (ml/g) N Kd value
(cm) value (ml/g)
(ml/g)
humus 10 - 4 368 34 10 460
top mineral
5-30 12 - 77 24 12 32
soil
intermediate
30-100 0.0 - 182 74 0.0 3.8
mineral soil
deep mineral
100-200 0.0 - 54 50 0.0 3.6
soil
deep mineral
>200 0.0 - 85 69 0.0 4.9
soil
79

Table 16. Continued.

Anaerobic soil
(cm) value (ml/g)
(ml/g)
intermediate
30-100 0.0 - 0.68 4 0.0 0.5
mineral soil
deep mineral
100-200 0.0 - 0.35 4 0.0 0.2
soil
deep mineral
>200 0.0 - 0.63 12 0.0 0.2
soil
4.4 Kd values for niobium
In nature the only oxidation state of niobium is +V. Only in very reducing conditions it
can be reduced to +IV state. Pentavalent niobium is expected to be present in water
solutions as Nb(OH)5 (or HNbO3) in slightly acidic to neutral media. At higher pH
values it may turn into Nb(OH)6- (or NbO3-), which has been expected to decrease its
sorption. As with other penta- and tetravalent metals niobium hydrolyses readily and is
thus fairly insoluble. Therefore, the sorption experiments with niobium are complicated
due to its tendency to sorb on various surfaces, not only on mineral surfaces but also on
surfaces of sorption experiment vials and filters. Experimental data on the sorption
behaviour of niobium in soil and other media is rather limited.
The sorption of niobium on aerobic untreated mineral soil samples of the excavator pit
OL-KK20 at about pH 4 is presented in Figure 50 and Appendix 8. The Kd values do
not show dependence on soil depth but the variation was rather wide, 15 385-127 414
ml/g. Reason for such behaviour is difficult to explain, as mineralogy, OM content, pH
and grain size distribution do not change notably between the samples. The average Kd
for the samples of OL-KK20 was 67 652 ml/g. In these experiments, the solution
equilibrium pH ranged between 3.2 and 4.5, and the average was 3.9.
Sorption and speciation of niobium in soil is rather poorly studied, but it has been noted
that niobium is relatively immobile in soils due to its strong sorption on mineral
particles (Echeverria et al. 2005). The sorption increases with decreasing particle size
(Sheppard et al. 1990), being effective on clay, and moderate or strong on sand and
gravel (Baston et al. 1992; Behrens et al. 1982). Compared with the literature results,
the experimental results in this study are in the same range or somewhat higher. The Kd
values reported in the literature ranged from 10 ml/g to 41 000 ml/g (Baker et al. 1994;
Baston et al. 1992; Behrens et al. 1982), compared with 15 385-127 414 ml/g
determined for the OL-KK20 samples at about pH 4.
80

0,5
1,0
1,5
Soil depth (m)

2,0
2,5
3,0
3,5
20000 40000 60000 80000 100000 120000 140000
Kd (ml/g)

Figure 50. Kd values for Nb-95 on the aerobic untreated soil samples of OL-KK20 at
about pH 4. The Kd values are calculated as an average of all the sorption test done to a
specific sample depth.
At pH values of 7-8 (Figure 51) the average Kd value of Nb-95 for the soil samples of
OL-KK20 was 60 573 ml/g, which is comparable with the value obtained at pH 4
(67 652 ml/g). Due to the tendency of niobium to sorb on various experimental surfaces,
additional tests were carried without filtering the liquids after equilibration. This yielded
a clearly lower average Kd value of 10 354 ml/g. The reason for this can be either that
the filters sorb dissolved niobium or filtering removes colloidal particles on which
niobium is adsorbed. In the former case filtering would overestimate Kd while in the
latter filtering would give a realistic value.
The Kd values showed slight dependence on soil depth (Figure 51), as Kd was the
highest in the topmost sample depth (0.7 m) and the lowest in the bottom sampling
depth (3.4 m). This behaviour was evident to both unfiltered and filtered samples.
However, the Kd values for filtered samples were noticeably higher than the Kd
determined from the unfiltered samples; 26 957-153 621 ml/g opposed to 5 042-20 397
ml/g, respectively. An increase in the Kd value upon filtering has previously been
explained as sorption of Nb on small suspended particles and colloids which are
removed from the solution upon filtering (Baker et al. 1994; Baston et al. 1992).
Therefore, blank experiments, where the sorption experiment procedure was repeated
without any solid material, were carried out. The decrease in the Nb-95 solution activity
of the blank samples upon filtering was only 2.1 %, whereas for the sorption samples
the decrease was from 43.9 % to 71.4 %. Thus, it was concluded that the higher Kd
values obtained upon filtering are due to the removal of colloidal particles bearing
niobium, and therefore these values are more representative.
This conclusion is also supported by the study of Baston et al. (1992), in which the Kd
values of Nb-95 on clay increased from 240-380 ml/g for unfiltered samples to 2100
ml/g and <10 000 ml/g for samples filtered through 0.45 µm and 0.03 µm filters,
respectively.
81

0,5
1,0
OL-KK20; unfiltered
Soil depth (m) 1,5 OL-KK20; filtered
2,0
2,5
3,0
3,5
0 20000 40000 60000 80000 100000 120000 140000 160000

Kd (ml/g)

Figure 51. Kd values for Nb-95 for unfiltered, centrifuged and filtered aerobic
untreated soil samples of OL-KK20 at pH 7-8. The Kd values are calculated as an
average of all the sorption test done to a specific sample depth.
Figure 52 presents Nb-95 Kd values for the untreated aerobic and anaerobic soil samples
of excavator pit OL-KK20 as a function of equilibrium pH. The pH does not have a
significant effect on the sorption of Nb-95, but a great variation between the different
samples is notable. For example, at pH values 3.6, 3.6 and 3.7 Kd values of 510 ml/g,
5 500 ml/g and 52 000 ml/g were observed. References for the sorption of niobium on
soil samples at different pH values were not available, but Anderson et al. (1979) found
that the sorption of niobium decreased with increasing pH in alkaline solutions when pH
was higher than 8. For example, Nb-95 Kd on Swedish granite decreased from 10 000
ml/g to 100 ml/g as the pH increased from 8.0 to 10.5. Such alkaline conditions were
not met in these sorption studies, but in the pH range 2.8-8.1 pH was not found to be a
dominant factor affecting the sorption of niobium on soil samples.
82

aerobic samples
anaerobic samples
Kd (ml/g)
100000
10000
1000
2,0 2,5 3,0 3,5 4,0 4,5 5,0 5,5 6,0 6,5 7,0 7,5 8,0 8,5

Figure 52. Kd values of Nb-95 for filtered aerobic and anaerobic soil samples of OL-
KK20 as a function of equilibrium pH. The concentration of pH buffer solution CHES in
the anaerobic samples was 1.0x10-3 M.
Sorption of Nb-95 on the untreated anaerobic mineral soil samples of OL-KK20 is

presented in Figure 53 and Appendix 8. The Kd is dependent on sample depth,
decreasing with increasing depth. For example, the Kd in the topmost sample depth (0.7
m) was 48 271 ml/g, whereas the corresponding value in the lowest sample depth (3.4
m) was 2 709 ml/g. The average Kd for the whole soil pit was 12 089 ml/g, and the
average pH was 5.69. Compared with the Kd values determined for the aerobic samples
at about pH 4, the anaerobic Kd values are significantly lower excluding sample depth
0.7 m, for which higher Kd was found (30 132 ml/g versus 48 271 ml/g). The average
Kd for the whole soil pit in the aerobic conditions was 67 652 ml/g, and the average pH
was 3.9. There was no clear correlation between the Kd values and pH (Fig. 52), and
thus the difference in the pH could not be reason for the discrepancy between aerobic
and anaerobic experiments.
83

0,5
1,0
1,5
Soil depth (m)
2,0
2,5
3,0
3,5
1000 10000 100000

Kd (ml/g)
Figure 53. Kd values for Nb-95 for anaerobic untreated soil samples of OL-KK20.
Samples contained CHES-buffer in 1.0x10-3 M concentration. The Kd values are
calculated as an average of all the sorption test done to a specific sample depth.
References for the sorption of niobium on soil samples in anaerobic conditions were not
available, but for granites the sorption preferred aerobic conditions (Andersson et al.
1979). The respective Kd values were approximately 10 000 ml/g and 1 200 ml/g at pH
8 for the aerobic and anaerobic conditions. The experimental results for the untreated
OL-KK20 mineral soil samples are similar to the results of the granite samples.
The Kd values for Nb-95 on the untreated humus samples of OL-KK21 are given in
Figure 54 and Appendix 8. The Kd values for the humus samples 1 and 3 increase
slightly as a function of time, excluding day one. The initial (1 day) and final (28 days)
Kd values for the unfiltered humus sample 1 are 990 ml/g and 1447 ml/g, whereas the
respective values for the humus sample 3 are 1077 ml/g and 1350 ml/g. The Kd values
calculated for the humus sample 2 somewhat decreased with time, as the Kd in day 1
was 781 ml/g and 669 ml/g on day 28. The pH values for the humus sample 2 was 1-1.5
pH units lower than for the humus samples 1 and 3. The Kd values for the filtered
samples are higher, which is explained as the sorption of Nb-95 on small, colloidal
particles. The difference in the activity of the blank experiments for unfiltered and
filtered samples was 2.1 %, whereas for the humus samples the difference ranged from
3.3 % to 6.3 %. Thus, it is concluded that the higher Kd values obtained upon filtering
the samples are more representative.
84

1800
1600
1400
1200 humus 1;
unfiltered
1000
humus 1;
filtered
Kd (ml/g)
humus 2;
800 unfiltered
humus 2;
filtered
humus 3;
600 unfiltered
humus 3;
filtered
400
0 5 10 15 20 25 30
Time (days)

Figure 54. Kd values of Nb-95 for unfiltered and filtered aerobic untreated humus
samples of OL-KK21 as a function of time.
The sharp decline in the Kd values after one day equilibrium time might be explained as
the bioaccumulation of Nb-95 into micro-organisms and liberation back to solution,
after which niobium is retained on present organic matter and mineral components. The
release of Nb-95 from micro-organism may be natural excretion or liberation due to the
perishing of the micro-organisms. Bioaccumulation is the active uptake of radionuclides
by living micro-organisms, which affects the biogeochemical cycle and sorption e.g. of
chloride (Bastviken et al. 2007; Kakiuchi et al. 2002). The variance in the sorption
behaviour of Nb-95 on the humus samples may be due to the differences in the sample
composition; the OM content was the highest for humus sample 2. If the organic matter
is the main sorbent for niobium and other factors had insignificant effect, the highest
sorption would have been seen for humus 2 samples. On the other hand, if the effect of
mineral matter would have been pronounced in the humus samples, the highest sorption
would naturally been seen for humus sample 3 having the highest dry matter content.
Average equilibrium pH of the unfiltered humus samples 1 and 3 were 7.1 and 7,
whereas the corresponding value for humus sample 2 was 5.3. The pH of the filtered
samples were typically approximately 0.1-0.5 pH units higher than for the unfiltered
samples. It is likely that one sole factor dominating the sorption reaction on humus
samples can not be named, but more factors act simultaneously.
Compared with the literature Kd values determined for peat and organic soils, the Kd
values in this study were almost at the same scale or considerably lower. The Kd value
of 14 000 ml/g for peat has been obtained by analysing the native element (stable Nb-
93) content from peat samples and their’s extracted pore water (Sheppard et al. 2009b),
while arithmetic mean value for organic soils has determined to be 2000 ml/g (Gil-
García et al. 2009; Sheppard & Thibault 1990; Vidal et al. 2009).
The sorption of niobium on humus samples is much lower than on anaerobic or aerobic
mineral soil samples. The average Kd for the unfiltered humus samples 1, 2 and 3 were
85

1066 ml/g, 623 ml/g and 915 ml/g, respectively, whereas the corresponding values were
12 089 ml/g (filtered) and 10 354 ml/g (unfiltered) for the anaerobic and aerobic mineral
soil samples. It has been suggested that the role of organic matter in the fixation of Nb
in soils may be substantial (Gerbazek et al. 1994), but based on the results of this study,
niobium is mainly retained in the mineral soil, more efficiently in aerobic soil
conditions than in anaerobic.
4.4.4 Recommendations of the Kd values for niobium
Figure 55 presents the Nb-95 Kd values as a function of soil depth on humus and
mineral soil samples. The data set for the humus comprised of the Kd values determined
for filtered OL-KK21 samples. The data set for mineral soil comprised of the Kd values
determined for the filtered soil samples of the excavator pit OL-KK20 conducted at
about pH 7-8. Filtered samples were used due to the tendency of niobium to sorb on
small suspended particles and colloids. The Kd values determined in pH of about 4 were
omitted because such a low pH is not typically met in soils. Also, the sorption tests
conducted in the anaerobic conditions were omitted because the formation of niobium-
CHES complex could not be ruled out. The range of the determined Kd values for the
humus and mineral soil samples in the sorption tests are given in Table 17, which also
presents the recommended conservative and realistic Kd values for niobium.
Soil depth:
humus
0 30-100 cm
100-200 cm
50 >200 cm
100
Soil depth (cm)
150
200
250
300
350
1000 10000 100000

Kd (ml/g)
Figure 55. Kd values of Nb-95 on the aerobic, filtered soil samples at about pH 7-8 of
OL-KK20 as a function of soil depth used in the estimation of the recommended
conservative and realistic Kd values.
The conservative and realistic Kd values of niobium on the humus are lower than on the
mineral soil in all soil depths. In the mineral soils the Kd values decrease with soil
depth. The best estimate values for niobium on Swedish soils ranged from 16 000 ml/g
to 940 000 ml/g depending on the soil type (Sheppard et al. 2009b). On the other hand,
the GM Kd values for loam and clay were 2 500 ml/g and 2 400 ml/g, respectively
86

(Vidal et al. 2009). Compared with these values, the recommended realistic Kd values
are approximately in the same range with GM Kd values for Swedish soils, but
considerably higher than the values estimated by Vidal et al. (2009).
Table 17. The range of the Kd values determined for Nb-95 in the sorption tests and
(cm) value (ml/g)
(ml/g)
humus 242 -1912 24 240 870
intermediate 19 587 –
30-100 8 19 500 100 000
mineral soil 4069 345
deep mineral 11 743 -
100-200 8 11 700 34 400
soil 112 837
deep mineral 2 172 -
>200 24 2100 23 500
soil 102 055
4.5 Kd values for selenium
Selenium is a non-metal and its chemistry resembles that of sulphur. The chemistry of
selenium is complicated due to several possible oxidation states of –II (selenide Se2-), 0
(elemental selenium S), +IV (selenite SeO32-) and +VI (selenate SeO42-). Selenate and
selenite occur in oxic conditions, elemental selenium in intermediate redox conditions
while selenide is the prevailing form in most reducing conditions. Selenate is sorbed on
mineral surfaces by ion exchange reaction whereas selenite can also form stronger
bonds by ligand exchange mechanism. Sorption of both forms is favoured by decreasing
pH due to an increase of negatively charged sorption sites on mineral surfaces. Selinide,
similarly to sulphide, forms sparingly soluble compounds with divalent transition metal
cations, especially with ferrous ions. Since the concentration of sulphur in soil is much
higher than that of selenium it is probable that selenide is coprecipitated with sulphide
compounds. Behaviour of elemental selenium is not well known. The initial speciation
of the selenium tracer used in the sorption experiments was selenite, but possible
transformations in the speciation during the sorption experiments were not studied.
Sorption of selenium on untreated, aerobic soil samples of OL-KK20 shows no clear

dependence on soil depth but lower Kd values in the two lowest sampling depths at 3.0
and 3.4 m were comparable (Figure 56, Appendix 9). The average Kd for the whole soil
pit calculated from all the unfiltered centrifuged samples was 95 ml/g. The Kd values
ranged from 9.5-244 ml/g and the highest Kd was in the uppermost sample depth at 0.7
m, whilst the smallest was in the lowest sample depth at 3.4 m. The difference between
the Kd values for unfiltered and filtered samples ranged from 1 ml/g to 15 ml/g
indicating that only minor, if any, fraction of selenium was sorbed on small suspended
particles or colloids.
87

0,5
1,0
OL-KK20; unfiltered
OL-KK20; filtered
1,5
Soil depth (m)
2,0
2,5
3,0
3,5
0 50 100 150 200 250 300

Kd (ml/g)

Figure 56. Kd values for Se-75 for the unfiltered, centrifuged and filtered aerobic
untreated soil samples of OL-KK20. The Kd values are calculated as an average of all
the sorption tests done to a specific sample depth.
The sorption of selenium on mineral soil increases with increasing organic matter (OM),
clay fraction, iron and aluminium oxyhydroxide contents, decreasing pH and with
enhanced weathering of the soil material (e.g. Choppin et al. 2009; Dhillon & Dhillon
1999; Dhillon et al. 2010; Keskinen et al. 2009; Neal et al. 1987; Pezzarossa et al. 1999;
Pezzarossa & Petruzelli 2001; Vuori et al. 1989; Yläranta 1983). Also, the role of
micro-organisms on the sorption of selenium on mineral soils has been found to be
important (Ashworth & Shaw 2006a; Darcheville et al. 2008; Février et al. 2007). The
OM content of the studied soil samples was rather equal and thus do not explain the
noticed sorption pattern. However, it is possible that in spite of the similar grain size
distribution of the samples, the composition of the fractions differed e.g. in the content
of weakly crystalline aluminium and iron oxides thus establishing the noted difference.
Solution equilibrium pH ranged between 6.7 in the uppermost layer and 8.0 in the
lowest layers. The Kd values increased with equilibration time up to nine weeks but no
essential increase was observed during the lats three weeks.
The effect of solution equilibrium pH on Se-75 Kd values is presented in Figure 57 for
all the soil samples of OL-KK20, both aerobic and anaerobic. The Kd values, their
uncertainties and equilibrium pH values are given in Appendix 9. There is no clear
correlation between increasing Kd and decreasing pH, as would be expected from the
increasing protonation degree of –M-OH groups to –M-OH2+ and arisen positive
surface charge of the mineral surfaces with decreasing pH (Choppin et al. 2009; Dhillon
& Dhillon 1999, Viers et al. 2001). Instead, rather constant Kd values around 200 ml/g
was observed at pH < 7.5, representing the pH values of soil samples at 0.7 m of OL-
KK20. A slight increase in the Kd is possible at the lowest measured pH values < 6. At
pH values 7.6-8.2, representative of the deeper mineral soil layers, the Kd values varied
from 2 ml/g to 650 ml/g. This reveals that another factor or factors than pH is
88

responsible for the variation; probably the cause is in the redox conditions. It is possible
that the highest Kd values in the uppermost sampling depth of 0.7 m are due to the lower
pH and higher OM content, but the reasons for the variation of the Kd values in the
deeper layers still remains unclear.
The experimental results of the Kd values in this study are in a good agreement with the
previous results of other researchers for different types of mineral soils. The Kd range of
1.3-1305 ml/g has been reported by Darcheville et al. (2008), Dhillon & Dhillon (1999),
Gil-García et al. (2009), Sharmasarkar & Vance (2002) and Vidal et al. (2009).
Typically the efficiency of fine textured soils to retain selenium is higher than that of
coarse textured soils, but the affinity of selenium towards organic matter is even higher
(Ashworth and Shaw 2006). For example, the Kd values of selenium on organic soil,
clay and sand were 1000, 240 and 56 ml/g, respectively (Vidal et al. 2009). Yläranta
(1983) determined the range for the selenium Kd values for Finnish fine sand soils to be
10.6 - 23.3 ml/g.
100
Kd (ml/g)
Aerobic;
centrifuged,
10
unfiltrated
Aerobic;
filtrated
Anaerobic;
filtrated
6,0 6,5 7,0 7,5 8,0 8,5

Figure 57. Kd values of Se-75 for the aerobic and anaerobic soil samples of OL-KK20
as a function of equilibrium pH.
The sorption behaviour of selenium in the anaerobic conditions does not differ
significantly from that in the aerobic conditions. The largest difference was that about
30-times lower Kd values were observed for soil depth 2.05 m in the anaerobic
conditions. At the other sample depths the differences were smaller (Figure 58).
Results from the anaerobic sorption tests are interesting, because typically the migration
rate and mobility decrease and retention increases in the anaerobic, reducing conditions
due to the formation of reduced forms of selenium; elemental selenium (Se(0)) and
selenide (Se(-II)) (Ashworth & Shaw 2006a). These forms are usually encountered in
the solid phase, whereas selenite (SeO32-(+IV)) and selenate (SeO42-(+VI)) are more
89

soluble and normally met in the liquid phase (Masschelyen et al. 1991; Pyrzyńska
1998). The sorption of selenite on minerals, soils and sediments is more efficient than
the sorption of selenate (Collins et al. 2006; Duc et al. 2003; Goldberger & Glaubig
1988; Sharmasarkar & Vance 2002). The transformations between the reduced and
oxidised forms of selenium in soils are usually relatively slow and can go through
microbiological or abiotoc route (Harada & Takahashi 2009; Ryser et al. 2006;
Zawilanski & Zavarin 1996). Altogether, micro-organisms have an important role in the
biogeochemistry, speciation and distribution of selenium in soils (Darcheville et al.
2008).
The average Eh of the samples of OL-KK20 was only +110 (range +60-200) RmV,
which is regarded as oxidizing environment. For example, the redox potential needed to
convert selenite to elemental selenium at pH 8-8.5 is 0- -50 mV (Takeno 2005). On
average, an increase of +88 RmV was noticed in the redox potential when comparing
the Eh values at seven days and 31 days equilibrium time. Based on the measured Eh
values and their changes, actually anaerobic, reducing conditions were not achieved.
The sorption of selenium in the anaerobic conditions needs more research so that
reliable and descriptive Kd values can be used in the migration modelling.
0,5
1,0
1,5
Soil depth (m)
2,0
2,5
3,0
3,5
1 10 100
Kd (ml/g)
Figure 58. Kd values of Se-75 for the filtered anaerobic untreated soil samples of OL-
KK20. The Kd values are calculated as an average of all the sorption test done to a
specific sample depth.
Kd values for mineral soils determined in anaerobic conditions were not found in the
literature. The Kd values for sea basin sediments in the anaerobic conditions have been
found to range from 412 ml/g to 9520 ml/g (Collins et al. 2006). Comparing with these
values, the Kd values in this study are significantly smaller (1.5-100 ml/g). The failure
to reach reducing conditions for the anaerobic soil samples is the probable reason for
such low Kd values. The relatively short time period used in our sorption tests could be
one of the reasons for rather high Eh values. The equilibrium time affects the redox
conditions of the samples by lowering the oxygen level in the nitrogen atmosphere of
the glovebox with time. Also, it is possible that any redox reactive components or pairs,
90

e.g. Fe3+ and Fe2+, were not present in the samples or their concentration was too low
for the redox potential to change. It is also possible that the Eh electrode could not track
the changes in the redox potential, and instead, the measured value was affected by the
pH.
The sorption of selenium on untreated humus samples 1, 2 and 3 of OL-KK21 increase

with time (Figure 59). For example, the Kd values for centrifuged, unfiltered samples of
humus sample 3 increased from 57 ml/g on day one to 785 ml/g on day 63. The increase
in the Kd values was even more drastic for humus sample 1, whereas for humus sample
2 the increase was only slight. The average Kd values for the humus samples 1, 2 and 3
were 419 ml/g, 298 ml/g and 313 ml/g, respectively. The average equilibrium pH values
for the respective samples were 6.9, 4.5 and 6.6.
Compared with the mineral soil samples, the Kd values of the humus samples were
fairly higher. The average Kd values for unfiltered/filtered aerobic samples and filtered
anaerobic samples were 95/101 ml/g and 35 ml/g, respectively, when the combined
average Kd for the unfiltered/filtered humus samples 1, 2 and 3 was 343/356 ml/g. The
results suggest that selenium is mainly retained in the soil layers rich with organic
matter, which is in good agreement with the previous studies where organic matter was
found to be the primary sorbent for selenium (e.g. Choppin et al. 2009; Gustafsson &
Johnsson 1992; Pezzarossa et al. 1999). The mechanism of association with organic
matter is proposed to be mediated by soil micro-organism, as micro-organisms reduce
selenium to lower oxidation states and enhance its sorption to humic substances
(Dhillon et al. 2010; Gustafsson and Johsson 1992). In soils, selenium is primarily
retained in the soil organic layer, topmost 0-4 cm, where the complex-forming
processes occur (Choppin et al. 2009; Gustafsson & Johnsson 1992; Lusa et al. 2009).
The retention of selenium on soils decreases with decreasing organic matter content
(Pezzarossa et al. 1999).
The Kd value of selenium in organic soils (organic matter content ≥ 20 %) ranged from
230 ml/g to 1800 ml/g (Gil-García et al. 2009; IAEA 1994; Sheppard & Thibault 1990;
Vidal et al. 2009). The Kd values attained in this study for humus samples, 57-1394
ml/g, are within these limits.
91

1600
1400
1200 humus 1;
unfiltered
humus 1;
1000
filtered
humus 2;
Kd (ml/g)
800 unfiltered
humus 2;
600 filtered
humus 3;
400 unfiltered
humus 3;
filtered
200
0 10 20 30 40 50 60 70
Time (days)
Figure 59. Kd values of Se-75 for the unfiltered, centrifuged and filtered aerobic
untreated humus samples of excavator pit OL-KK21 as a function of time.
4.5.4 Recommendations of the Kd values for selenium
Figure 60 presents the aerobic Se-75 Kd values as a function of soil depth on humus and
mineral soil samples of OL-KK20. The data set for the humus comprised of the Kd
values determined from the filtered samples of OL-KK21. The data set for the mineral
soil consisted of the Kd values determined from the filtered soil samples of OL-KK20.
On the other hand, the estimation of the recommended conservative and realistic Kd
values for Se-75 on the anaerobic Olkiluoto soils was based on the data set of the Kd
values determined for the anaerobic OL-KK20 mineral soil samples in the anaerobic
conditions. The range of the determined Kd values for the humus and mineral soil
samples in the sorption tests are given in Table 18, which also presents the
recommended conservative and realistic Kd values for selenium in the aerobic and
anaerobic conditions.
The realistic Kd value of selenium for humus was approximately equal with the
uppermost aerobic mineral soil (30-100 cm), but considerably higher than for deeper
mineral soil layers (Table 18). The respective values for anaerobic soil decreased with
soil depth. Anaerobic conditions are probably prevailing at soil depths below 100 cm or
at least 200 cm.
The best estimate values for selenium on Swedish soils ranged from 85 ml/g to 360 ml/g
depending on the soil type (Sheppard et al. 2009b). On the other hand, the geometric
mean Kd values for sand, loam and clay were 56 ml/g, 220 ml/g and 240 ml/g,
respectively (Vidal et al. 2009). Compared with these values, the recommended realistic
Kd values are in the same range.
92

50
Soil depth:
100
humus
30-100 cm
100-200 cm
Soil depth (cm)
150
>200 cm
200
250
300
350
0 200 400 600 800 1000 1200 1400 1600 1800

Kd (ml/g)
Figure 60. Kd values of Se-75 on the aerobic, filtered soil samples of OL-KK20 as a
function of soil depth used in the estimation of the recommended conservative and
realistic Kd values.
Table 18. The range of the Kd values determined for Se-75 in the sorption tests and
Aerobic soil
Soil depth Kd range Conservative Realistic Kd
Soil type N
(cm) (ml/g) Kd value (ml/g) value (ml/g)
57 –
humus 36 57 240
1 669
intermediate
30-100 180 - 464 16 180 250
mineral soil
deep mineral
100-200 2.26 - 408 16 2.2 17
soil
deep mineral
>200 2.44 - 654 48 2.4 17
soil
Anaerobic soil
Soil type N
intermediate
30-100 85 - 116 4 85 116
mineral soil
deep mineral
100-200 20 - 101 4 20 46
soil
deep mineral
>200 1.36 - 28 12 1.4 4.7
soil
93

4.6 Kd values for technetium
Technetium occurs in aerobic conditions as an anionic species of TcO4- (pertechnetate)

with the oxidation state of +VII. At low redox potentials pertechnetate is reduced to
tetravalent Tc4+ which is readily hydrolysable and thus forms insoluble
oxides/hydroxides or is strongly sorbed on hydroxyl groups on mineral surfaces.
Pertechnetate, in turn, is very mobile and does not pratically interact with mineral
surfaces due to its large size and low negative charge. In the experiments of this study
technetium was initially added in the pertechnetate form.
The sorption of technetium in the pertechnetate (TcO4-) form on dried and fractioned
soil samples of different soil layers of OL-KK14, OL-KK15 and OL-KK16 is presented
in Figure 61 and Appendix 10. In OL-KK14 and OL-KK15 the highest Kd values were
for the humus layer, 15.1 ml/g and 126 ml/g, respectively, whereas in OL-KK16 the Kd
in the humus layer, 1.44 ml/g, was at same level as in the mineral soil layers. The low
Kd value for OL-KK16 humus sample may be due to its high pH, 6.2, compared with
the pH values 5.0 and 4.6 for OL-KK14 and OL-KK15, respectively. In mineral soil
layers the average Kd values were 0.50 ml/g, 0.12 ml/g 1.00 ml/g for OL-KK14, OL-
KK15 and OL-KK16, respectively, and there was no trend with soil depth.
humus
OL-KK14
MS1 OL-KK15
Soil layer
OL-KK16
MS2
MS3
MS4
MS5
1 10 100
Kd (ml/g)

Figure 61. Kd values of Tc-99 for the soil layers of OL-KK14, OL-KK15 and OL-KK16.
The Kd values for each sample depth was calculated as a weighted average of the Kd
values determined for the grain size fractions of >0.063 mm, 0.063-0.125 mm, 0.125-
0.25 mm, 0.25-0.50 mm, 0.50-1.0 mm and 1.0-2.0 mm. Negative Kd values are not
shown on logarithmic scale.
94

Literature references concerning the determination of the Kd values of technetium on

soil samples taken at different sampling depths done as extensively as in this study was
not available. The Kd values determined for soils, observed in the previous studies,
ranged from -0.4 ml/g to 61 ml/g, whilst the typical Kd was approximately 0-0.5 ml/g
(Abdelouas et al. 2002; Mousny & Myttenaere 1981; Sheppard et al. 1990; Vidal et al.
2009). The Kd values determined in this study are in good agreement with the literature
results. It is worth noting that the samples used in the sorption experiments were dried
and fractioned and the Kd values for the soil layers were calculated as a weighted
average of the Kd values of the studied grain sizes (>0.063 mm, 0.063-0.125 mm, 0.125-
0.25 mm, 0.25-0.50 mm, 0.50-1.0 mm and 1.0-2.0 mm). The overall average Kd values
for the deep soil pits were 3.42 ml/g, 21.1 ml/g and 1.08 ml/g for OL-KK14, OL-KK15
and OL-KK16, respectively.
The sorption of technetium on mineral soil is known to be quite low and to be mostly or
completely reversible ion exchange on soils’ sorption sites (Bunzl & Schimmack 1988;
Denys et al. 2003; Koch-Steindl & Pröhl 2001; Lieser & Bauscher 1987; Sheppard et al.
1983). In mineral soils, aluminium and iron sesquioxides may act as sorbents for
technetium (Mousny & Myttenaere 1981; Tagami & Uchida 1996). The presence of
competing anions hinders the sorption as the competition of the sorption sites increases
(Lieser & Bauscher 1987).
The sorption of technetium (TcO4-) on untreated aerobic soil samples of OL-KK20
shows no clear dependence on soil depth, organic matter content or equilibrium pH
(Figure 62, Appendix 10). The average Kd value for the soil pit OL-KK20 was 1.32
ml/g, which is slightly higher than the average Kd values for mineral soil layers of OL-
KK14, OL-KK15 and OL-KK16; 0.50 ml/g, 0.35 ml/g and 1.00 ml/g, respectively. The
reason might be that the soil samples of OL-KK20 were not dried before the sorption
experiments, and thus contained more micro-organisms capable of changing the
ambient Eh-pH conditions by decomposing organic matter in the presence of limited
amounts of oxygen (Abdelouas et al. 2002, 2005; Koch-Steindl & Pröhl 2001). Shift in
the redox conditions to more reducing would induce a change in the speciation of
technetium from highly mobile and non-sorbing pertechnetate (TcO4-) to immobile,
sparingly soluble Tc(+IV) (Lieser & Bauscher 1987). In dried and pretreated samples
the microbe population might be reduced in comparison with the untreated soil samples.
The typical Kd value for technetium on mineral soil has been reported to be
approximately 0-0.5 ml/g with the range from -0.4 ml/g to 61 ml/g (Abdelouas et al.
2002; Mousny & Myttenaere 1981; Sheppard et al. 1990; Vidal et al. 2009). The Kd
values determined in this study are within these ranges.
95

0,5
1,0
1,5
Soil depth (m)

2,0
2,5
3,0
3,5
1,2 1,3 1,4

Kd (ml/g)

Figure 62. Kd values of Tc-99 for the aerobic untreated soil samples of OL-KK20. The
Kd values were calculated as an average of all the sorption test done to a specific
sample depth.
The Kd values determined for dried and fractioned soil samples are not recommended to
be used in the migration modelling of technetium because they may not represent the
actual conditions in the natural environment. Instead, the Kd values for untreated soil
samples may give more relevant results even though the difference between untreated
and pretreated samples was only minor.
4.6.3 Anaerobic untreated soil samples of OL-KK20 and OL-KK21
Technetium is a redox sensitive element and in anaerobic, reducing conditions

formation of rather immobile, sparingly soluble Tc(+IV) species is dominating (Koch-
Steindl & Pröhl 2001; Lieser & Bauscher 1987). Tc(+IV) has high affinity towards
surface sorption sites which increases the Kd value of technetium (Lieser & Bauscher
1987). The mobility of technetium in oxygen deficient soils is very low or non-existing
(Ashworth & Shaw 2005; Lieser & Bauscher 1987; Tagami & Uchida 1996; Tagami &
Uchida 1999). At pH 7, the conversion from TcO4- to Tc(+IV) takes place when the
redox potential is approximately +100 mV, whereas at pH 9 the conversion occurs at
lower redox potentials (0 mV) (Takeno 2005).
Figure 63 and Appendix 10 presents the Kd values of technetium on untreated anaerobic
soil samples of OL-KK20 and OL-KK21. Sorption on the samples of OL-KK21 clearly
increases with soil depth, whereas on OL-KK20 the sorption shows only slight
variation. The retention of technetium on OL-KK21 samples was higher than on the
samples of OL-KK20, excluding sample depth 1.1 m. Reason for the higher Kd values
for OL-KK21 are probably the lower measured redox potentials compared with OL-
KK20; +46.28-133.66 RmV versus +202.48-366.48 RmV. The highest Kd value
determined for OL-KK21 was seen for the lowest sample depth 3.6 m (568 ml/g),
whereas sample depth 1.1 m had the lowest value (1.05 ml/g). In OL-KK20, the Kd
values remained almost constant ranging from 0.86 ml/g to 3.04 ml/g. The average Kd
96

value for the soil pits OL-KK20 and OL-KK21 were 1.96 ml/g and 93.6 ml/g, whereas
the respective average Eh values were +253.6 RmV and +93.6 RmV. It is probable that
the reduction on pertechnetate to Tc(+IV) took place in the more reducing samples
leading to higher Kd values. In this experiment series highly reducing conditions were
not met.
OL-KK20
0,0
OL-KK21
0,5
1,0
Soil depth (m)
1,5
2,0
2,5
3,0
3,5
4,0
1 10 100
Kd (ml/g)

Figure 63. Kd values of Tc-99 for the anaerobic untreated soil samples of OL-KK20 and
OL-KK21. The Kd values were calculated as an average of all the sorption test done to
a specific sample depth.
For OL-KK20, the difference in the sorption behaviour of technetium between the
aerobic and anaerobic samples was practically nonexisting, the average Kd values being
1.32 ml/g and 1.96 ml/g, respectively. This is probably due to the rather high Eh value
of +253 RmV in the anaerobic conditions. However, for OL-KK21 the Kd values
determined for the anaerobic samples were considerably higher compared with the
values of the aerobic samples indicating the substantial role of the redox conditions and
speciation on the sorption of technetium. The redox conditions and its effect on the
speciation of technetium in soils overwhelm the effect of organic matter in the retention
and sorption processes.
In anaerobic soil conditions the Kd values of technetium has reported being in the range
of 0.27-440 ml/g (Sheppard et al. 1990). The results of this study are in a good
agreement with the literature values, even though some further research is
recommendable to carry out, especially in the anaerobic conditions.
Organic matter is known as the main sorbent for oxidised and reduced technetium
species in soils (Ashworth & Shaw 2005; Bunzl & Schimmack 1988; Koch-Steindl &
Pröhl 2001; Mousny & Myttenaere 1981; Sheppard et al. 1983; Sheppard et al. 1990).
97

The sorption reaction is reversible and not affected by pH in the range of 1.6-5.4
(Wolfrum & Bunzl 1986).
The sorption of technetium (TcO4-) on humus sample 1 increased with increasing
equilibrium time; from 3.54 ml/g on day seven to 366 ml/g on day 31 (Figure 64,
Appendix 10). Equilibrium pH remained from neutral (7.0) to slightly alkaline (7.7). It
is known that aerobic micro-organisms are not able to reduce or biosorb TcO4- (Bennett
& Willey 2003), so the behaviour for untreated humus samples is due to changes in
other properties. It is possible that micro-organisms have induced changes e.g. in the
redox conditions since TcO4- does not form complexes with humic substances, and
complexation occurs only when TcO4- is reduced to Tc(+IV) (Bennett & Willey 2003;
Ticknor et al. 1996). The reduction reaction increases the sorption of technetium on
humic substances, and also enhances the association of Tc with solid organic matter,
which would explain the rather high Kd values were observed with time.
1000
100
Kd (ml/g)
10
1
0 20 40 60 80 100
Time (days)

Figure 64. Kd values of Tc-99 for the untreated humus sample 1 of OL-KK21 as a
function of time.
The Kd values for the dried and fractioned humus samples of OL-KK14, OL-KK15 and
OL-KK16 were considerably smaller than the values for OL-KK21, namely 15.1 ml/g,
126 ml/g and 1.44 ml/g compared with 306 ml/g. Reason for the low sorption on dried
and fractioned samples may be caused by a decrease in the microbe population during
the sample drying. The Kd values determined for organic soils by other researchers have
been in the range of 1.5-41 ml/g (Kaplan 2003; Vidal et al. 2009; Wolfrum & Bunzl
1986). The values in this study are substantially higher in comparison with the literature
values, which may be e.g. due to longer equilibrium times used in this experiment
series.
The sorption of technetium on untreated irradiation sterilized humus samples 1, 2 and 3

of OL-KK21 increase with equilibrium time (Appendix 10), but do not extend to the
same level with nonsterilized soil samples. The Kd values for irradiated samples
98

increased from 2.89 ml/g on day seven to 9.50 ml/g on day 93. Equilibrium pH ranged
from 4.80 to 5.68. The Kd values determined for irradiated humus samples resemble the
values determined for the dried and fractioned humus samples, for which the Kd values
ranged from 1.44 ml/g to 126 ml/g. For untreated humus samples the average Kd was
306 ml/g. These results support the role of micro-organism in the retention of
technetium on soil, and corroborate the hypothesis that soil micro-organisms induce a
decrease in the soil redox potential upon which TcO4- is reduced to Tc(+IV) and
associated with dissolved humic substances and solid organic matter. From the
literature, the Kd values for irradiated peat were approximately 7-20 ml/g (Bunzl &
Schimmack 1988).
4.6.6 Recommendations of the Kd values for technetium
Figure 65 presents the Tc-99 Kd values as a function of soil depth on humus and mineral
soil samples. The data set for the humus samples comprised of the Kd values determined
for OL-KK14, OL-KK15, OL-KK16 and OL-K21. The Kd values determined for
irradiation sterilized samples were not included in the humus data set because microbial
activity is typically ubiquitous in all type of soils soils. The data set for the aerobic
mineral soil consisted of the Kd values determined for the aerobic soil samples of OL-
KK14, OL-KK15, OL-KK16, OL-KK20 and OL-KK21. The derivation of the
recommended conservative and realistic Kd values for Tc-99 in the anaerobic conditions
was based on the data set of the Kd values determined for the anaerobic OL-KK20 and
OL-KK21 mineral soil samples (Figure 66). The range of the determined Kd values for
humus and mineral soil is given in Table 19, which also presents the recommended
conservative and realistic Kd values for technetium in the aerobic and anaerobic
conditions.
50 Soil depth:
humus
100 5-30 cm
30-100 cm
100-200 cm
Soil depth (cm)
150
>200 cm
200
250
300
350
0,01 0,1 1 10 100

Kd (ml/g)
Figure 65. Kd values of Tc-99 on the aerobic soil samples of OL-KK14, OL-KK15, OL-
KK16, OL-KK20 and OL-KK21 as a function of soil depth used in the estimation of the
99

0 Soil depth:
30-100 cm
50 100-200 cm
>200 cm
100
Soil depth (cm)
150
200
250
300
350
0,1 1 10 100 1000

Kd (ml/g)
Figure 66. Kd values of Tc-99 on the anaerobic soil samples of OL-KK20 and OL-KK21
as a function of soil depth used in the estimation of the recommended conservative and
realistic Kd values.
The conservative Kd values for humus, aerobic and anaerobic mineral soil was 0.0 ml/g.
The estimated realistic technetium Kd value was rather high for humus, 21 ml/g,
whereas the corresponding value for aerobic mineral soil ranged from 0.4 ml/g to 0.7
ml/g. The realistic Kd values calculated for anaerobic mineral soil were about ten times
higher than for the aerobic mineral soil showing no clear dependence on soil depth.
Previously Vidal et al. (2009) estimated that the geometric mean Kd value of technetium
on organic soil was 3.1 ml/g, whereas the corresponding values for sand, loam and clay
were 0.04 ml/g, 0.07 ml/g, and 0.09 ml/g, respectively. On the other hand, Sheppard et
al. (2009b) estimated the overall geometric mean Kd value for technetium on aerated
soil to be 3.1 ml/g, whereas the respective value for anaerobic soils was 65 ml/g. The
recommended realistic Kd values for aerobic mineral soils presented in this report are
within the same range with the values estimated by Vidal et al (2009), but remain
smaller than the 3.1 ml/g assessed by Sheppard et al (2009b). The geometric mean Kd
value of 21 ml/g for humus is higher than the value (3.1ml/g) proposed by Vidal et al.
(2009). Furthermore, the recommended Kd values for technetium in the anaerobic soil
conditions are smaller than the value of 65 ml/g estimated by Sheppard et al (2009b).
100

Table 19. The range of the Kd values determined for Tc-99 in the sorption tests and
Aerobic soil
Soil type N
humus 0.0 - 578 45 0.0 21
top mineral
5-30 0.0 - 2.41 15 0.0 0.4
soil
intermediate
30-100 0.0 - 6.29 62 0.0 0.6
mineral soil
deep mineral
100-200 0.0 - 3.01 43 0.0 0.6
soil
deep mineral
>200 0.0 - 8.97 60 0.0 0.7
soil
Anaerobic soil
Soil type N
intermediate
30-100 0.0 - 93 14 0.0 9.3
mineral soil
deep mineral
100-200 0.0 - 145 23 0.0 3.0
soil
deep mineral
>200 0.0 - 3680 41 0.0 7.9
soil
101

5 SUMMARY
Biosphere (dose) assessment programme for the spent nuclear fuel is focused on Cl-36,
I-129, C-14, Mo-93, Nb-94, Cs-135, Ni-59, Se-79 and Sr-90 (Hjerpe et al. 2010, p. 36-
38; Haapanen et al. 2009, p. 22-23).
The source for I-129 and Tc-99 in the spent nuclear fuel is the fission of U-235 and Pu-
239 atoms. Cl-36, Nb-94 and Se-79 are long-lived activation products formed from the
stable isotopes present in the nuclear fuel, structural components and construction
materials used in the power reactors. Nb-94 and Se-79 are also fission products.
Knowledge of the behaviour of these nuclides in the environment is of notable interest
because of their long physical half-lives and anionic nature. Cs-135 is also a fission
product, which exists solely in the cationic form. The interest in Cs-135 arises from its
long physical half-life.
The sorption of radionuclides in soils is affected by parameters specific to the element
and to the soil. Chemical form, speciation, is the most important elemental factor
affecting the sorption and migration properties of the element. Soil redox potential, pH
and complex forming ligands are features that have a great influence on the speciation.
Micro-organisms can affect the speciation of radionuclides indirectly by changing the
prevailing Eh-pH conditions and also serve as sorbents. Organic matter content and soil
mineral composition have a noticeable influence on the retention of radionuclides.
Radionuclides having a high tendency of forming anionic species in aqueous solutions,
such as chlorine, iodine, selenium and technetium, are poorly sorbed on soil mineral
constituents and thus have a high potential mobility in the overburden. The sink for
anionic radionuclides, such as iodine and selenium, is most likely the organic matter.
Cationic nuclides may be effectively associated with the soil mineral matter, depending
on the mineral composition.
Distribution coefficient, Kd, is used to describe the retention of a substance on the solid
phase. Kd value is defined as the concentration ratio of the radionuclide between the
solid and liquid phases in the equilibrium state. High Kd values indicate the
considerable retention of radionuclide on soil or sediment, whereas for low Kd values
the retention is small. Kd is widely used as an indicator of the mobility of radionuclides
in the environment.
The sorption of caesium, chlorine, iodine, niobium, selenium and technetium was
studied on aerobic and anaerobic Olkiluoto soil samples in experimental batch sorption
tests to gain site specific knowledge on their retention.
Soil chemical and geotechnical characteristics
The chemical and geotechnical analyses for soil samples of OL-KK20 and OL-KK21
were carried out. The main results are:
 The pH and dry matter content increased as a function of depth, whereas organic
matter content decreased.
 The main minerals in the mineral soil samples were quartz, plagioclase,
potassium feldspar and kaolinite in the grain size fractions <0.01 mm and 1.0-
2.0 mm. Small amounts of micas, amphibole, hematite and chlorite were found.
102

 Cation exchange capacity showed significant variation among the sampling

depths (due to the different soil types). CECs ranged from 63 mmol/kg to 287
mmol/kg in OL-KK20. The respective variation in OL-KK21 was 64-218
mmol/kg.
 The specific surface area was the highest in the smallest grain size fraction
<0.063 mm for OL-KK14, ranging from 2.1 m2/g to 9.0 m2/g. The specific
surface for the mineral soil layers decreased in the order
MS2>MS3>MS4>MS1. In OL-KK20 and OL-KK21 the specific surface area
decreased with depth. The range in OL-KK20 was 0.8-6.8 m2/g and 0.9-4.0 m2/g
in OL-KK21.
Caesium
Caesium was retained efficiently on the mineral soil samples. For the soil pits OL-
KK14, OL-KK15 and OL-KK16 the Kd values decreased as a function of depth
corresponding to a decrease in the clay fraction content and CEC. Kd for the topmost
mineral soil layer MS1 was smaller than for the underlying MS2 layer in OL-KK14 and
OL-KK15. For the mineral soil layers, the Kd values ranged approximately between
3 000 ml/g and 33 000 ml/g. The retention was the smallest in the humus layers, where
the Kd value range was 200-12 000 ml/g.
The sorption of caesium on the aerobic untreated soil samples of OL-KK20 and OL-
KK21 was smaller than for the dried and fractioned mineral soil samples of OL-KK14,
OL-KK15 and OL-KK16. The mineral soil samples of OL-KK21 retained caesium
better than the samples of OL-KK20. The Kd values varied between 1 300 ml/g and
7 300 ml/g. Sorption in the anaerobic conditions was reduced probably due to an
increase in the NH4+ concentration and thus pronounced competition of the sorption
sites. The Kd values decreased from 1 300-5 500 ml/g in the aerobic conditions to 650-
3 300 ml/g in the anaerobic conditions.
Humus was not sorbing caesium efficiently. Sorption decreased with time from 6 600
ml/g on day seven to 1 800 ml/g on day 23. The reason for this could be a possible
decrease in the microbe population due to decline in the oxygen and nutrient
concentration with increasing equilibrium time.
The effect of competing cations decreased in the order Cs+>NH4+>K+>Ca2+>Na+. In the
concentration of 10 mM stable Cs+, the Kd values decreased to <1 ml/g, whereas in
1000 mM Na+ solutions the Kd values were still >50 ml/g indicating very weak
competition between caesium and sodium of the soil sorption sites. The effect of
ammonium and potassium ions were similar and resulted in smaller Kd values compared
with the soil solution simulant even in 0.1 mM K+ or NH4+ concentration. The effect of
calcium was similar to that of sodium.
Chlorine
Retention of chloride anion on mineral soil samples did not take place; the Kd values
were approximately 0 ml/g. Sorption on the untreated humus samples was minor, and
the sorption slightly decreased with increasing equilibrium time. The Kd values ranged
from 0 ml/g to 1.70 ml/g. Irradiation sterilisation did not have a marked effect on the
retention of chlorine on humus. On dried and fractioned humus samples of OL-KK15,
103

the sorption increased with time and the highest Kd value 61 ml/g was determined for
the smallest grain size fraction <0.063 mm.
Iodine
The Kd values of iodine for dried and fractioned humus samples of OL-KK14 and OL-
KK15 were rather high, 604 ml/g and 2670 ml/g, respectively. For OL-KK16 the Kd
was slightly lower, approximately 78 ml/g. The retention of iodine decreased in the
mineral soil layers as a function of depth with decreasing organic matter content and
increasing equilibrium pH.
The sorption of iodine was higher on untreated mineral soil samples of OL-KK20 and
OL-KK21 than on dried and fractioned soil samples of OL-KK14, OL-KK15 and OL-
KK16. One of the reasons may be the decrease in the microbe population for the
fractioned samples caused by sample pretreating (drying). The Kd values for OL-KK20
ranged from 14.2 ml/g to 26.4 ml/g, while the respective variation for OL-KK21 was
5.90-136 ml/g. Iodine did not sorb on the anaerobic mineral soil samples and the Kd
values remained practically at 0 ml/g. Probably the speciation of iodine as poorly
retaining iodide (I-) or the negative surface charge of the mineral soil induced by the
high equilibrium pH resulted in the low sorption.
Untreated humus samples of OL-KK21 retained iodine quite well even though sorption
on dried and fractioned humus samples was higher. The Kd values declined as a
function of equilibrium time from 475 ml/g on day five to 9.6 ml/g on day 93. It is
possible that the decrease in the sorption was due to the decay in the microbe population
induced by the consumption of oxygen and nutrients. This is supported by the fact that
the sorption of iodine on irradiation sterilised humus samples was comparably smaller;
the Kd values were only 2.50-10.40 ml/g on day seven whereas for nonsterilized humus
sample the respective value was 244 ml/g. It is also possible that irradiation has induced
some changes in the sample composition, for example increase the solubility of the
fulvic/humic acids.
Niobium
Among the studied elements, niobium retained on the mineral soil samples the most
efficiently. Sorption experiments in the aerobic conditions with untreated mineral soil
samples of OL-KK20 was conducted at two different pH value ranges. At the lower pH
range of 3.2 to 4.5, the Kd varied randomly with respect to depth between 15 000 ml/g
and 127 000 ml/g. At the higher pH values between 6.8 and 7.9, the Kd values were in
the range 27 000-154 000 ml/g. The highest values were found for the uppermost
sampling depth of 0.70 m. The Kd values determined from the filtered samples were
higher than the values for centrifuged samples, which was due to the sorption of Nb-95
on colloidal material removed by filtering. The fraction of direct filter sorption was
notably smaller. The Kd values for centrifuged and filtered samples were 5 000-20 000
ml/g and 27 000-154 000 ml/g, respectively.
Sorption of niobium on anaerobic mineral soil samples of OL-KK20 was studied at the
pH range of 5.3-6.1. The Kd value in the uppermost soil depth (0.7 m) was
approximately at the same level as in the aerobic conditions (48 000 ml/g), but at the
104

deeper layers the difference in the Kd values was approximately one order of magnitude
lower.
The retention of niobium on untreated humus samples of OL-KK21 was smaller than on
the mineral soil samples. The highest Kd value was approximately 1 800 ml/g whilst the
typical Kd was below 1 000 ml/g and somewhat increased with time.
Selenium
The Kd values for selenium on the aerobic soil samples of OL-KK20 had no clear
dependence on soil depth. The highest Kd for the centrifuged samples was 244 ml/g at
the sample depth 0.70 m, whereas the lowest was 9.50 ml/g at 3.00 m depth. In the
anaerobic conditions the sorption of selenium decreased with soil depth from 98 ml/g at
0.70 m to approximately 5 ml/g at 2.05 m and 3.00 m depths. In the anaerobic samples
the sorption of selenium decreased with time.
Organic matter is the main sorbent for selenium in soils which is indicated by the
elevated Kd values for humus compared with the mineral soil samples. Retention
increased with time, for example from 67 ml/g on day one to 1 400 ml/g on day 63 for
the humus sample 1 of OL-KK21.
Technetium
The retention of technetium is the highest on soil layers enriched with organic matter. In
the soil layers of OL-KK14, OL-KK15 and OL-KK16, the Kd values decreased from
15.1 ml/g, 126 ml/g and 1.44 ml/g in the humus layer to <1 ml/g in the mineral soil
layers. In the aerobic mineral soil samples of OL-KK20 the Kd values were
approximately 1.3 ml/g.
In the anaerobic conditions the sorption of technetium increased with decreasing redox
potential due to the reduction of highly mobile pertechnetate anion (TcO4-) to sparingly
soluble Tc(+IV) species. This was seen as relatively high Kd values for mineral soil
samples of OL-KK21, up to 570 ml/g. There was no clear dependency with the sorption
and soil depth, but typically the Kd values were higher for the soil samples taken from
the soil pit’s deepest parts (2.40-3.60 m). For the soil pit OL-KK20, the redox
conditions remained quite oxidising and, thus low Kd values, around 2.0 ml/g, were
observed.
The retention of technetium increased as a function of time on untreated humus samples
of OL-KK21; Kd value on day seven was 3.54 ml/g and 547 ml/g on day 93. The
highest value (547 ml/g) is comparable to the highest values in the anaerobic conditions
(570 ml/g). Irradiation sterilisation decreased considerably the retention of technetium
on humus, for example, the Kd value for the humus sample 3 was only 7.40 ml/g on day
93. Thus, the effect of micro-organisms may be crucial to soil redox conditions and the
retention of technetium on soils.
Final conclusions
Caesium and niobium are retained very efficiently on mineral soil regardless of the
prevailing redox conditions and thus their migration to overlaying biosphere is greatly
hindered.
105

Technetium, and possibly also selenium are retained very well and immobilised in the
reducing soil regime due to the formation of reduced, sparingly soluble species Tc(+IV)
and Se(0,-II). Once oxidising conditions come prevailing, Tc(+IV) and Se(0,-II) are
oxidised to more mobile forms TcO4- and SeO32- and SeO42- and migrated upwards
within the soil profile by diffusion and with the groundwater flow. In the uppermost
parts of the soil profiles technetium and selenium are retained in the soil layers enriched
with organic matter.
Iodine is very poorly sorbing in anaerobic, reducing mineral soil conditions where the
prevailing species is iodide (I-). Iodine continues the upward migration until a soil layer
enriched with organic matter is encountered. In this layer, iodine is retained and its
further migration is delayed in some extent.
Chlorine is sorbed poorly on mineral and humus soil layers. Thus, the migration of Cl-
36 is not supposed to be inhibited at any time and it is freely distributed into the
biosphere.
Based on the results presented in this work, the most important radionuclides in the
safety assessment of spent nuclear fuel are Cl-36 and I-129 irrespective the soil
conditions. Se-79 and Tc-99 are considered less mobile and important as far as the
conditions remain reducing. Upon oxidation, these elements become mobile and their
importance in the safety assessment increases. Caesium and niobium are considered the
least important of the studied elements due to their effective sorption on mineral soil.
Table 20 summarises the processes taking place in soil and their effect on the studied
radionuclides.
Table 20. The effect of processes taking place in soil on Cs-135, Cl-36, I-125, Nb-94,
Se-75 and Tc-99.
Process Cs-135 Cl-36 I-125 Nb-94 Se-75 Tc-99
Retention on organic matter + + + + + +
Retention on clay minerals/
clay soils + ± + ± ± ±
Retention on weakly
crystalline Al and Fe oxides ± ± + ±
Retention by carbonates ± + +
Retention by reducing
minerals (e.g. pyrite) ± ± ±
Retention by micro-
organisms ± ± + ± ± +
Incorporation into organic
substances (by micro- ± ± ± ± ±
organisms)
High pH + ± - - - -
Formation of precipitates ±
Volatilization ± ±
Decrease in the redox +
potential (aerobic → - - - +
anaerobic)
+ process seen in Olkiluoto samples; correlation with retention is positive
- process seen in Olkiluoto samples; correlation with retention is negative
± process not seen/verified in Olkiluoto samples
positive correlation with retention in the literature negative correlation with retention in the literature
indirect negative correlation with retention in the literature process is not important/does not take place
(enough) information not available in the literature
106

107

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123

APPENDIX 1. OL-KK20 and OL-KK21 soil pH
OL-KK20 OL-KK21
soil depth aerobic samples anaerobic samples soil depth aerobic samples anaerobic samples
(m) (m)
pH Milli-Q pH CaCl2 pH Milli-Q pH CaCl2 pH Milli-Q pH CaCl2 pH Milli-Q pH CaCl2
0.7 7.9 7.1 8.6 8.0 0.121 6.8 6.0 - -
1.3 7.8 7.1 9.3 8.5 0.122 5.3 4.6 - -
2.05 7.7 6.9 9.6 8.7 0.123 6.6 6.2 - -
3.0 7.7 6.9 9.5 8.5 0.4 6.2 5.6 7.3 6.6
3.4 7.8 6.9 9.6 9.5 1.1 7.4 6.6 8.2 7.5
123
- - - - - 1.75 8.3 7.4 8.8 7.8

- - - - - 2.4 8.5 7.6 9.0 7.9
- - - - - 2.95 8.3 7.5 9.1 7.8
- - - - - 3.6 8.4 7.6 9.1 8.0
1
0.12 humus sample 1 of the excavator pit OL-KK21
- sample not taken
124

APPENDIX 2. OL-KK20 and OL-KK21 organic and dry matter content
OL-KK20 OL-KK21
aerobic samples anaerobic samples aerobic samples anaerobic samples

soil depth organic organic soil depth organic organic
(m) dry matter dry matter (m) dry matter dry matter
matter matter matter matter
content content content content
content content content content
(%) (%) (%) (%)
(%) (%) (%) (%)
0.7 0.8 85.7 0.8 92.2 0.121 11.2 28.6 - -
1.3 0.6 91.8 0.6 94.9 0.122 14.2 34.4 - -
2.05 0.4 91.8 0.4 94.8 0.123 9.6 39.0 - -
124
3.0 0.4 92.0 0.4 93.5 0.4 1.1 87.5 1.3 89.7
3.4 0.5 92.0 0.4 94.9 1.1 0.7 90.1 0.9 93.3
- - - - - 1.75 0.5 91.0 0.6 92.9
- - - - - 2.4 0.4 91.7 0.5 93.3
- - - - - 2.95 0.4 90.5 0.5 94.6
- - - - - 3.6 0.3 89.9 0.4 91.6
1
- sample not taken
125

APPENDIX 3. OL-KK20 and OL-KK21 mineralogy
Appendix 3.1. Mineralogy of the aerobic soil samples of the excavator pit OL-KK20.
Grain size <0.01 mm
soil depth (m) Minerals
Quartz (%) Potassium Plagioclase Kaolinite (%) Mica (%) Amphibole Hematite (%)
feldspar (%) (%) (%)
0.7 45 10 30 10 <5 + (+)
1.3** 50 15 25 10 <5 + (+)
2.05 45 10 30 10 <5 + (+)
3.0 35 25 30 10 <5 + (+)
3.4* 50 10 25 10 <5 + (+)
Grain size 1.0-2.0 mm
soil depth (m) Minerals
Quartz (%) Potassium Plagioclase Kaolinite (%) Mica (%) Amphibole Hematite (%)
125
feldspar (%) (%) (%)

0.7 60 10 15 10 <5 + (+)
1.3 60 15 25 <5 <5 ‐ ‐
2.05 50 20 25 5 <5 ‐ ‐
3.0 45 25 20 10 <5 (+) (+)
3.4 45 25 20 10 <5 ‐ ‐
* sample heated in 550 °C for one hour
** sample heated in 550 °C for one hour and IR spectrum was measured
(+) possibly
126

APPENDIX 3. OL-KK20 and OL-KK21 mineralogy
Appendix 3.2. Mineralogy of the aerobic soil samples of the excavator pit OL-KK21.
Grain size <0.01 mm
soil depth Minerals
(m) Potassium
Quartz Plagioclase Kaolinite Amphibole Hematite Chlorite
feldspar Mica (%)
(%) (%) (%) (%) (%) (%)
(%)
0.4 45 15 30 10 <5 (+) (+) -
1.1* 45 15 30 10 <5 + (+) -
1.75 45 15 25 10 5 + (+) -
2.4 50 10 30 5 <5 + (+) -
2.95** 50 10 30 5 <5 + (+) +
3.6 50 15 25 5 <5 + (+) -
126
Grain size <0.01 mm

Minerals
soil depth Potassium
Quartz Plagioclase Kaolinite Amphibole Hematite Chlorite
(m) feldspar Mica (%)
(%) (%) (%) (%) (%) (%)
(%)
0.4 55 20 20 5 <5 - - -
1.1 45 25 20 10 <5 - - -
1.75 55 20 25 - - - - -
2.4 55 15 25 5 <5 - - -
2.95 55 15 25 5 <5 - - -
3.6 65 10 15 5 <5 - - -
* sample heated in 550°C for one hour
** sample heated in 550°C for one hour and IR spectrum was measured
(+) possibly
127
127

APPENDIX 4. OL-KK14, OL-KK20 and OL-KK21 specific surface areas
Appendix 4.1. Specific surface areas of soil samples of the excavator pit OL-KK14.
Soil layer Grain size (mm) Specific surface area (m2/g)
MS1 <0.063 2.1
0.063-0.125 1.0
0.125-0.25 1.1
0.25-0.50 0.9
0.50-1.0 0.7
1.0-2.0 0.6
MS2 <0.063 9.0
0.063-0.125 4.6
0.125-0.25 6.9
0.25-0.50 7.2
0.50-1.0 6.8
1.0-2.0 5.6
MS3 <0.063 7.2
0.063-0.125 3.5
0.125-0.25 3.2
0.25-0.50 3.8
0.50-1.0 3.7
1.0-2.0 3.4
MS4 <0.063 5.2
0.063-0.125 2.6
0.125-0.25 2.3
0.25-0.50 2.9
0.50-1.0 3.9
1.0-2.0 4.1
128
128

APPENDIX 4. OL-KK14, OL-KK20 and OL-KK21 specific surface areas
Appendix 4.2. Specific surface areas of soil samples of the excavator pits OL-KK20 and
OL-KK21.
OL-KK20 OL-KK21
Specific surface Specific surface
Soil depth (m) 2 Soil depth (m)
area (m /g) area (m2/g)
0.7 6.8 0.4 3.5
1.3 2.5 1.1 4.0
2.05 1.4 1.75 2.7
3.0 1.0 2.4 1.0
3.4 0.8 2.95 1.0
- - 3.6 0.9
- sample not taken
129

APPENDIX 5. Kd values of caesium
Appendix 5.1. Kd values of caesium for the soil layers of the excavator pits OL-KK14, OL-KK15 and OL-KK16.
OL-KK14 OL-KK15 OL-KK16

Soil
layer Geometric Geometric Geometric
sample sample sample
Kd standard Kd standard Kd standard
depth pH depth pH depth pH
(ml/g) deviation (ml/g) deviation (ml/g) deviation
(cm) (cm) (cm)
(ml/g) (ml/g) (ml/g)
humus 5 11 759 10 355 4.7 7 198 152 4.5 10 964 835 5.6
MS1 20 3 041 369 5.2 50 982 153 6.8 30 11 228 733 7.1
MS2 60 32 787 4 650 6.5 80 18 949 2162 7.3 50 8 906 121 7.3
MS3 105 13 969 6.9 110 7 864 7.9 110 6 942 8.0
129
2 109 095 679

MS4 240 4 192 575 7.5 160 5 396 827 8.0 300 3 157 394 8.3
MS5 - - - - 260 2 936 437 8.6 - - - -
- sample not taken
130

Appendix 5.2. Kd values of caesium for the different grain sizes of the soil layers of the
excavator pit OL-KK15.
Soil layer Grain size Standard
(mm) Kd (ml/g) deviation pH
(ml/g)
humus <0.063 584 450 4.6
0.063-0.125 127 3.5 4.6
0.125-0.25 124 1.6 4.4
0.25-0.50 112 3.8 4.5
0.50-1.0 126 7.4 4.5
1.0-2.0 115 1.3 4.5
MS1 <0.063 6 937 3 098 6.5
0.063-0.125 1 832 199 6.6
0.125-0.25 1 123 161 6.6
0.25-0.50 1 002 51 6.9
0.50-1.0 722 47 7.0
1.0-2.0 610 53 7.1
MS2 <0.063 18 408 528 7.3
0.063-0.125 11 058 391 7.2
0.125-0.25 19 767 53 7.3
0.25-0.50 20 457 1 219 7.3
0.50-1.0 18 823 1 028 7.3
1.0-2.0 17 898 311 7.5
MS3 <0.063 11 264 186 7.9
0.063-0.125 5 955 261 7.8
0.125-0.25 5 695 63 7.9
0.25-0.50 6 343 197 7.9
0.50-1.0 7 853 282 8.0
1.0-2.0 6 412 605 8.0
MS4 <0.063 7 057 195 8.0
0.063-0.125 4 443 38 8.0
0.125-0.25 4 783 277 7.9
0.25-0.50 4 956 181 8.0
0.50-1.0 5 095 265 8.0
1.0-2.0 4 835 259 8.0
MS5 <0.063 4 060 71 8.1
0.063-0.125 2 157 81 8.4
0.125-0.25 1 780 75 8.7
0.25-0.50 1 622 21 8.7
0.50-1.0 2 790 172 8.8
1.0-2.0 6 093 659 8.8
131

Appendix 5.3. Kd values of caesium for the excavator pits OL-KK20 aerobic and anaerobic and OL-KK21 aerobic soil samples.
OL-KK20 OL-KK21
aerobic anaerobic aerobic
Soil
Geometric Geometric Geometric
depth Soil
standard standard Eh standard
(m) Kd (ml/g) pH Kd (ml/g) pH depth Kd (ml/g) pH
deviation deviation (RmV) deviation
(m)
0.7 5 456 7.6 7.6 3 319 3 146 8.6 343 0.4 7 256 7 200 7.3
1.3 2 661 8.1 8.1 2 093 978 9.2 60 1.1 5 327 5 211 7.6
2.05 1 680 8.1 8.1 1 038 016 9.5 22 1.75 3 666 3 660 8.0
3.0 19 17 8.1 8.1 1 047 026 9.6 30 2.4 3 559 2 623 7.9
3.4 1 315 8.2 8.2 649 620 9.6 29 2.95 2 400 2 330 7.8
131
- - - - - - - - 3.6 2 742 2 132 7.9

- sample not taken
132

Appendix 5.4. Kd values of caesium for the excavator pit OL-KK20 aerobic and anaerobic soil samples.
OL-KK20 Aerobic
Time
1 3 5 7
(days)
Soil Standard Standard Standard Standard
depth Kd (ml/g) deviation pH Kd (ml/g) deviation pH Kd (ml/g) deviation pH Kd (ml/g) deviation pH
(m) (ml/g) (ml/g) (ml/g) (ml/g)
0.7 3 422 399 7.0 4 114 623 8.6 4 886 624 7.7 4 184 1 429 7.5
1.3 1 709 7.5 7.6 2 252 284 9.1 2 201 29 7.9 2 115 924 7.4
2.05 902 28 7.7 1 317 32 9.1 1 154 13 7.9 1 526 600 7.7
3.0 810 5.6 7.6 1 234 29 9.2 1 590 208 7.8 728 78 8.1
3.4 663 74 7.6 920 30 9.1 1 101 45 7.9 580 152 8.3
OL-KK20 Aerobic OL-KK20 Anaerobic
Time
21 42 245 1
(days)
Soil Standard Standard Kd error Standard
132
Kd Eh
depth Kd (ml/g) deviation pH Kd (ml/g) deviation pH Kd (ml/g) 2σ pH deviation pH
(ml/g) (RmV)
0.7 6 235 3121 5.8 5 066 380 5.6 4 891 187 5.7 2 429 1 069 8.9 360
1.3 2 214 65 5.9 2 803 310 6.4 2 743 1 730 6.1 1 887 232 9.5 216
2.05 1 569 361 5.9 1 728 159 6.1 1 851 352 6.1 781 327 9.7 173
3.0 1 732 368 5.9 1 852 578 6.1 3 207 2 387 6.1 827 43 9.8 193
3.4 1 119 239 5.9 1 204 189 6.5 2 136 1 651 6.1 354 6.0 9.8 178
OL-KK20 Anaerobic
Time
3 5 7 28
(days)
Kd Eh Kd Eh Kd Eh Kd Eh
depth deviation pH deviation pH deviation pH deviation pH
(ml/g) (RmV) (ml/g) (RmV) (ml/g) (RmV) (ml/g) (RmV)
(m) (ml/g)) (ml/g) (ml/g) (ml/g)
0.7 2 368 97 8.7 387 3 135 555 8.7 289 3 781 998 8.5 337 4 884 248 8.4 342
1.3 1 191 503 9.3 149 2 535 754 9.2 -36 2 094 230 9.1 -31 2 759 435 8.9 1.5
2.05 1 051 79 9.6 52 1 075 81 9.6 -49 1 024 52 9.4 -55 1 258 4.4 9.2 -11
3.0 991 33 9.6 48 950 158 9.5 -42 1 070 212 9.5 -47 1 399 201 9.3 -3.5
3.4 727 26 9.7 46 604 92 9.7 -39 744 84 9.6 -43 817 210 9.4 3.5
133

Appendix 5.5. Kd values of caesium for the excavator pit OL-KK21 aerobic soil samples.
Time
1 3 5 7
(days)
0.4 6392 1 339 7.0 6 958 1 183 7.6 8 160 90 7.6 7 166 806 7.25
1.1 3413 17 7.3 3 979 293 8.3 4 495 448 7.8 5 042 360 7.48
1.75 2390 56 7.7 2 894 25 8.9 3 723 380 8.0 3 890 317 7.73
2.4 1160 92 7.5 1 832 10 8.4 2 859 879 7.9 1 902 213 7.69
2.95 1300 54 7.5 1 879 210 7.9 1 885 224 7.9 2 104 323 7.69
3.6 738 13 7.5 1 477 60 8.0 2 353 537 8.0 1 453 168 7.61
Time
21 42 112 AVERAGE
(days)
Geometric
Soil Standard Standard Standard
standard
depth Kd (ml/g) deviation pH Kd (ml/g) deviation pH Kd (ml/g) deviation pH Kd (ml/g) pH
133
deviation
(m) (ml/g) (ml/g) (ml/g)
(ml/g)
0.4 6944 976 7.4 6 940 1 126 7.3 8 230 638 6.9 7 256 7 200 7.28
1.1 4609 778 7.7 5 703 248 7.5 10 047 1 111 7.3 5 327 5 211 7.63
1.75 4071 177 7.8 3 679 569 7.8 5 014 2 311 7.8 3 666 3 660 7.97
2.4 2699 153 7.8 3 023 1 396 7.8 11 433 12 502 8.0 3 558 2 623 7.87
2.95 2556 71 7.8 2 564 654 7.8 4 514 474 7.8 2 400 2 330 7.78
3.6 2063 154 7.9 3 075 567 7.9 8 037 6 802 8.1 2 742 2 132 7.85
134

Appendix 5.6. Kd values of caesium for the excavator pit OL-KK20 aerobic soil samples in the presence of stable Cs, Na or K competing
cation.
CsCl 0.01 0.1 1 10 Soil solution simulant
concentration
(mM)
Standard Standard Standard Standard Standard
Soil depth Kd Kd Kd Kd Kd
deviation pH deviation pH deviation pH deviation pH deviation pH
(m) (ml/g) (ml/g) (ml/g) (ml/g) (ml/g)
(ml/g) (ml/g) (ml/g) (ml/g) (ml/g)
0.7 215 0.9 7.2 72.1 6.8 7.1 15.6 7.2 7.1 1.05 0.4 7.9 4 184 1 429 7.46
1.3 53.3 0.9 7.6 15.6 3.3 7.6 5.27 0.6 7.5 0.79 0.5 7.5 2 115 924 7.41
2.05 46.7 13 7.6 9.51 1.2 7.6 3.52 0.5 7.6 0.38 0.3 7.6 1 526 600 7.71
3.0 40.4 7.2 7.8 11.0 0. 7.7 4.13 0.5 7.6 0.87 0.1 7.7 728 78 8.12
3.4 49.3 9.2 7.8 10.3 0.1 7.7 3.56 0.2 7.7 0.92 0.2 7.6 580 152 8.3
NaCl 0.1 1 10 100 1000
concentration
(mM)
134

0.7 8 892 6288 7.2 8 312 825 7.1 2 744 32 7.2 826 198 7.1 163 29 6.66
1.3 4 624 228 7.6 4 502 53 7.6 1 851 315 7.7 520 110 7.9 93.9 11 8.82
2.05 1 349 297 7.7 1 655 453 7.7 893 43 7.8 299 15 7.9 64.1 2.9 8.88
3.0 1 015 94 7.7 1 894 412 7.6 824 38 7.8 280 16 7.9 70.7 9.0 8.71
3.4 1 720 81 7.8 822 44 7.8 923 156 7.7 235 9.1 8.0 55.3 6.1 8.87
KCl 0.1 1 10 100 1000
concentration
(mM)
0.7 3 032 359 7.7 27524 4519 7.3 752 128 7.0 9.49 1.0 7.2 -11.4 0.1 7.31
1.3 1 286 107 7.4 246 13 7.4 27.9 0.9 7.2 -7.89 0.7 8.3 -11.9 0.1 8.87
2.05 601 60 7.5 110 17 7.3 8.60 0.9 7.6 -9.93 0.4 8.3 -12.1 0.1 8.67
3.0 666 51 7.5 130 23 7.5 6.78 0.2 7.7 -9.97 0.4 8.7 -11.9 0.1 8.9
3.4 521 19 7.6 90.3 3.3 7.5 6.80 5.5 7.9 -10.3 0.8 8.6 -943 2.8 8.79
135

Appendix 5.6. Kd values of caesium for the excavator pit OL-KK20 aerobic soil samples in the presence of NH4 or Ca as competing cation.
NH4Cl 0.1 1 10 100 1000
concentration
(mM)
0.7 1281 20 6.4 7 143 9 297 7.3 164 23 7.2 5.83 1.5 7.2 -0.42 0.5 7.2
1.3 574 89 7.3 120 5.1 8.2 12.4 0.6 8.2 -2.16 3.1 7.8 -3.60 3.7 8.2
2.05 407 92 6.7 115 82 7.4 7.98 0.3 7.4 -0.25 0.1 7.5 -1.06 0.6 7.4
3.0 8 801 1 165 7.1 292 340 7.9 9.58 1.1 7.8 2.71 2.6 7.7 -0.18 0.1 7.9
3.4 399 46 7.4 44.2 2.9 8.1 6.43 0.1 8.2 0.45 0.1 8.0 -0.03 0.1 8.0
CaCl2 0.1 1 10 100 1000
concentration
(mM)
135

0.7 5 371 1 004 6.3 3 722 346 6.6 1580 13 6.7 707 45 6.7 238 24 6.6
1.3 2 193 150 7.2 1 601 350 7.4 1280 54 7.6 506 27 7.8 138 7.4 7.6
2.05 1 115 312 6.7 1 000 193 6.9 989 379 7.1 483 2.7 7.1 101 2.4 7.0
3.0 1 415 76 6.8 1 089 20 6.8 921 19 7.2 430 31 7.1 91.4 0.8 7.1
3.4 861 0.6 7.4 750 67 7.7 530 116 7.9 296 94 7.9 61.4 5.6 6.7
136

APPENDIX 6. Kd values of chlorine
Appendix 6.1. Kd values of chlorine for the excavator pit OL-KK15 dried and fractioned
humus samples.
0.25 months
Grain size (mm) Standard deviation
Kd (ml/g) pH
(ml/g)
<0.063 -0.12 0.3 4.5
0.063-0.125 -0.07 0.5 4.4
0.125-0.25 0.00 0.1 4.3
0.25-0.50 0.02 0.1 4.2
0.50-1.0 0.20 0.1 4.2
1.0-2.0 -0.20 0.1 4.2
>2.0 -0.45 0.2 4.2
3 months
Grain size (mm) Standard deviation
Kd (ml/g) pH
(ml/g)
<0.063 60.9 0.5 4.5
0.063-0.125 19.8 0.8 4.4
0.125-0.25 30.1 0.1 4.3
0.25-0.50 30.4 0.6 4.3
0.50-1.0 29.5 1.0 4.4
1.0-2.0 27.3 0.7 4.3
>2.0 27.8 1.3 4.3
137

APPENDIX 6. Kd values of chlorine
Appendix 6.2. Kd values of chlorine for the excavator pit OL-KK21 untreated and irradiated humus samples 1, 2 and 3.
Untreated humus samples
Time Humus 1 Humus 2 Humus 3
(days) Standard Standard Standard
Kd (ml/g) deviation pH Kd (ml/g) deviation pH Kd (ml/g) deviation pH
7 0.96 0.1 6.7 0.82 0.4 5.5 0.75 0.1 7.1
29 0.68 0.1 7.0 0.49 0.2 6.0 0.73 0.1 7.2
93 0.95 0.1 8.5 1.67 0.4 5.9 1.00 0.3 7.0
186 0.89 0.1 7.8 - - - - - -
365 0.31 0.1 7.7 1.42 0.4 6.7 0.46 0.1 7.7
Untreated, irradiation sterilized humus samples
137
Time Humus 1 Humus 2 Humus 3

(days) Standard Standard Standard
Kd (ml/g) deviation pH Kd (ml/g) deviation pH Kd (ml/g) deviation pH
7 1.55 0.4 5.5 0.88 0.1 4.8 1.24 0.1 6.8
93 -4.13 7.6 5.7 0.80 0.4 4.7 1.18 0.9 6.3
- sample not done
138

APPENDIX 7. Kd values of iodine
Appendix 7.1. Kd values of iodine for the soil layers of the excavator pits OL-KK14, OL-KK15 and OL-KK16.

Soil
(cm) (cm) (cm)
humus 5 604 536 4.7 7 2 670 2572 4.4 10 78 47 5.5
MS1 20 55 8.4 5.4 50 2.1 0.3 6.7 30 18 2.9 7.1
MS2 60 1.5 0.2 6.9 80 1.1 0.1 7.4 50 7.7 0.9 7.3
MS3 105 0.5 7.2 110 0.03 8.2 110 2.7 8.3
138
0.1 0.1 0.4

MS4 240 0.1 0.1 7.9 160 0.2 0.1 8.1 300 1.1 0.1 8.5
MS5 - - - - 260 -0.6 0.1 8.6 - - - -
- sample not taken
139

Appendix 7.2. Kd values of iodine for dried and fractioned humus samples of the excavator pits OL-KK14, OL-KK15 and OL-KK16.
Grain size Standard Standard Standard
(mm) Kd (ml/g) deviation pH Kd (ml/g) deviation pH Kd (ml/g) deviation pH
<0.063 359 17 4.7 3799 805 4.5 - - -
0.063-0.125 389 41 4.8 2045 133 4.5 163 33 5.6
0.125-0.25 460 71 4.7 2 303 372 4.5 144 64 5.6
0.25-0.50 1242 78 4.7 1 867 214 4.4 47 0.8 5.5
0.50-1.0 786 154 4.8 2 715 434 4.4 24 12 5.5
1.0-2.0 387 8.0 4.7 3 290 158 4.4 10 0.1 5.4
- sample not done (no material left)
139
140

Appendix 7.3. Kd values of iodine for the excavator pits OL-KK20 aerobic and anaerobic and OL-KK21 aerobic soil samples.
OL-KK20 OL-KK21
aerobic anaerobic aerobic
Soil
Geometric Geometric Geometric
depth Soil
standard standard Eh standard
(m) Kd (ml/g) pH Kd (ml/g) pH depth Kd (ml/g) pH
deviation deviation (RmV) deviation
(m)
0.7 26 17 7.4 -0.1 0.5 9.0 379 0.4 136 133 7.4
1.3 18 12 7.9 -0.4 0.2 9.6 261 1.1 22 18 7.7
2.05 26 12 7.9 -0.1 0.2 9.7 252 1.75 6.0 5.0 7.9
3.0 14 9.8 7.8 -0.03 0.2 9.7 247 2.4 7.8 4.6 8.0
140
3.4 19 11 7.9 -0.4 0.2 9.8 240 2.95 5.9 4.6 7.9
- - - - - - - - 3.6 12 8.0 8.0
- sample not taken
141

Appendix 7.4. Kd values of iodine for the excavator pit OL-KK21 untreated and untreated, irradiated humus samples 1, 2 and 3.
Time Humus 1
(days) Kd (ml/g) Standard deviation (ml/g) pH
1 233 8.2 7.5
3 344 19 7.4
5 475 0.5 7.3
7 244 288 7.0
21 17 0.6 7.7
93 9.6 1.0 7.6
141

Humus 1 Humus 2 Humus 3
Time Standard Standard Standard
(days) Kd (ml/g) deviation pH Kd (ml/g) deviation pH Kd (ml/g) deviation pH
7 2.5 0.2 5.7 6.0 0.5 4.8 10 11 5.5
93 63 5.9 5.6 48 28 5.3 59 0.6 5.5
142

APPENDIX 8. Kd values of niobium
Appendix 8.1. Kd values of niobium for the excavator pit OL-KK20 aerobic and anaerobic soil samples.
OL-KK20 aerobic; tracer in 0.5 M HNO3 + 0.3 M HF, filtered
Time
7 21 42 63
(days)
0.7 5 554 4 171 3.6 45 754 2 410 2.8 41 955 4 212 2.9 5 1843 2 457 3.2
1.3 27 040 27 952 5.6 14 590 859 3.3 23 919 7 972 3.8 54 4483 642 098 3.9
2.05 14 098 13 354 4.4 15 940 989 2.9 14 856 1 116 3.3 17 933 2 204 3.3
3.0 16 613 11 927 4.8 17 274 1 470 2.9 424 143 560 741 4.3 13 733 477 3.2
3.4 18 375 20 506 5.1 20 711 5 981 2.7 52 303 38 011 3.7 12 530 2998 3.6
OL-KK20 aerobic; tracer in 0.1 M HCl, filtered
Time
7 21 42 63
(days)
142
0.7 184 463 32 633 5.3 19 781 274 7.2 100 533 49 308 7.4 309 709 137 498 7.2
1.3 100 720 17 136 7.5 13 222 2 092 8.0 28 709 3 096 7.9 39 284 17 753 8.0
2.05 68 654 7 406 7.5 17 253 8 114 7.9 29 676 7 748 8.0 36 995 16 659 8.1
3.0 55 141 4 702 7.4 2 788 871 7.9 21 141 4 895 7.8 28 757 6 317 8.0
3.4 53 929 37 364 7.4 3 641 1 099 8.0 28 874 2 464 8.0 68 185 47 900 8.0
OL-KK20 anaerobic; tracer in 0.5 M HNO3 + 0.3 M HF, 1.0x10-3 M CHES, filtered
Time 1 3 7 21
(days)
Kd Eh Kd Eh Eh Eh
depth deviation pH deviation pH Kd (ml/g) deviation pH Kd (ml/g) deviation pH
(ml/g) (RmV) (ml/g) (RmV) (RmV) (RmV)
0.7 6 323 13 04 4.5 453 5 737 1 610 5.1 462 788 166 1 061 229 5.5 333 102 995 58 600 5.8 450
1.3 7 412 55 5.8 249 2 276 318 5.6 308 6 982 1 640 6.4 194 7 699 1 046 7.0 129
2.05 469 31 5.4 261 1 148 470 6.0 224 4 669 2 567 6.4 191 5 366 1 743 6.5 165
3.0 359 27 5.1 295 725 26 5.6 246 3 653 81 6.2 203 6 772 160 6.3 182
3.4 510 119 3.6 425 1 069 61 3.9 410 2 049 565 5.8 240 5 588 1 635 6.1 202
143

Appendix 8.2. Kd values of niobium for the aerobic and anaerobic soil samples of the
Aerobic; 0.5 M HNO3 + 0.3 M HF, filtered
Geometric
Soil depth (m) Kd (ml/g) standard pH Eh (RmV)
deviation (ml/g)
0.7 30 132 17 753 3.2 -
1.3 127 414 29 835 4.5 -
2.05 15 385 12 630 3.7 -
3.0 97 675 21 060 4.0 -
3.4 24 459 17 248 4.0 -
Aerobic; tracer 0.1 M HCl, centrifuged, unfiltered
0.7 20 397 19 078 6.9 -
1.3 9 091 7 800 7.6 -
2.05 10 018 8 627 7.7 -
3.0 7 223 5 783 7.7 -
3.4 5 042 4 077 7.6 -
Aerobic; tracer 0.1 M HCl, filtered
0.7 153 621 100 093 6.8 -
1.3 45 484 34 397 7.9 -
2.05 38 145 32 671 7.9 -
3.0 26 957 17 256 7.8 -
3.4 38 657 23 110 7.8 -
Anaerobic; tracer 0.5 M HNO3 + 0.3 M HF, 1.0x10-3 M CHES, filtered
0.7 48 271 29 901 5.3 425
1.3 3 862 3 068 6.0 220
2.05 2 670 1 844 6.1 210
3.0 2 935 1 592 5.7 232
3.4 2 709 1 559 5.3 319
- not measured
144

Appendix 8.3. Kd values of niobium for the untreated humus samples 1, 2 and 3 of
Humus 1
Time Centrifuged, unfiltered Filtered
(days) Standard Standard
Kd (ml/g) deviation pH Kd (ml/g) deviation pH
(ml/g) (ml/g)
1 990 497 7.0 1054 485.6788 7.2
3 859 687 7.1 918 731.2094 7.5
7 969 224 7.1 1014 155.8739 7.2
28 1447 62 7.2 1768 202.8191 7.3
Humus 2
(ml/g) (ml/g)
1 781 477 5.1 811 502 5.1
3 614 114 5.1 664 145 5.4
7 429 286 5.3 455 300 5.4
28 669 590 5.6 756 689 5.6
Humus 3
(ml/g) (ml/g)
1 1077 219 7.1 1098 225 7.3
3 568 315 6.9 589 335 7.3
7 663 70 7.0 699 54 7.1
28 1350 33 6.9 1447 80 7.0
145

APPENDIX 9. Kd values of selenium
Appendix 9.1. Kd values of selenium for the aerobic and anaerobic soil samples of the
Aerobic; centrifuged, unfiltered
Geometric
Soil depth (m) Kd (ml/g) standard pH Eh (RmV)
deviation (ml/g)
0.7 244 237 6.7 -
1.3 51.5 17 7.9 -
2.05 160 76 8.0 -
3.0 9.50 8.2 7.9 -
3.4 10.6 7.0 8.0 -
Aerobic; filtered
0.7 258 250 6.7 -
1.3 54.9 17 8.0 -
2.05 170 78 8.0 -
3.0 9.68 8.3 7.9 -
3.4 11.2 7.3 8.0 -
Anaerobic; filtered
0.7 98.2 97 7.0 202
1.3 53.6 46 8.0 88
2.05 5.00 4.6 8.1 60
3.0 5.23 3.9 8.1 86
3.4 12.8 6.0 7.9 131
- not measured
146

Appendix 9.2. Kd values of selenium for the excavator pit OL-KK20 aerobic and anaerobic soil samples.
OL-KK20 aerobic; centrifuged, unfiltered
Time 7 21 42 63
(days)
Soil Standard
Kd Standard Standard deviation Standard deviation
depth deviation pH Kd (ml/g) pH Kd (ml/g) pH Kd (ml/g) pH
(ml/g) deviation (ml/g) (ml/g) (ml/g)
(m) (ml/g)
0.7 195 19 7.1 221 246 25 28 6.8 6.5 232 229 2.49 35 6.6 6.8 233 390 11 89 7.0 6.0
1.3 5.4 3.1 7.8 9.1 16.7 3.2 4.1 8.0 7.6 8.3 314 0.43 97 8.0 8.1 15 36.8 4.8 13 8.1 7.7
2.05 22 10 7.9 26 272 9.3 321 8.0 7.8 588 88.5 0.59 5.5 8.0 8.1 98 170 20 16 8.0 8.1
3.0 4.2 1.3 7.8 5.8 9.99 0.3 0.8 7.9 7.8 8.5 19.2 0.40 1.9 8.0 7.8 7.5 15.9 2.5 0.7 8.0 7.8
3.4 3.7 1.3 7.9 4.4 9.79 0.1 3.1 7.9 7.8 5.2 21.9 0.39 18 8.0 8.1 6.4 29.4 0.7 31 8.0 8.1
OL-KK20 aerobic; filtered
Time 7 21 42 63
(days)
Soil Standard
Kd Standard Standard deviation Standard deviation
depth deviation pH Kd (ml/g) pH Kd (ml/g) pH Kd (ml/g) pH
(ml/g) deviation (ml/g) (ml/g) (ml/g)
146
(m) (ml/g))
0.7 204 27 7.1 223 251 26 23 6.7 6.5 234 314 18 39 6.6 6.64 237 395 11 97 6.8 6.0
1.3 5.6 3.0 7.9 9.1 16.9 3.2 3.8 8.0 8.0 8.6 341 0.6 95 8.05 8.14 15 37.3 4.8 12 8.1 8.1
2.05 20 9.0 7.9 27 292 9.7 346 8.0 7.9 627 91.0 38 5.0 7.97 8.09 98 182 20.1 20 8.0 8.1
3.0 4.6 1.5 7.9 5.8 10.2 0.4 0.7 8.0 7.8 8.8 19.7 3.1 1.7 7.97 8.03 7.5 16.3 2.6 0.7 8.0 8.0
3.4 3.9 0.7 7.9 4.5 10.0 0.2 3.3 8.0 7.9 5.2 23.4 0.2 20 8.02 8.09 6.5 31.8 0.4 344 8.0 8.2
OL-KK20 anaerobic; filtered
Time 7 31
(days)
Soil
depth Kd (ml/g) Standard deviation (ml/g) pH Eh (RmV) Kd (ml/g) Standard deviation (ml/g) pH Eh (RmV)
(m)
0.7 100 2.24 6.9 77 95.9 14 7.1 261
1.3 33.3 1.13 8.1 47 74.0 0.3 8.3 88
2.05 6.94 0.70 8.0 67 3.06 2.8 8.3 84
3.0 8.68 0.72 7.8 5.5 1.79 3.6 8.5 120
3.4 24.2 0.96 7.7 13 1.50 19 8.6 219
147

Appendix 9.3. Kd values of selenium for the humus samples 1, 2 and 3 of the excavator
pit OL-KK21.
Humus 1
(ml/g) (ml/g)
1 67 1.4 6.8 67 2.2 6.8
3 99 6.2 6.7 100 5.6 6.8
7 174 93 6.9 177 95 7.0
21 302 0.9 6.7 306 1.6 6.8
42 475 28 7.1 485 33 7.3
63 1 394 156 7.3 1 519 212 7.3
Humus 2
(ml/g) (ml/g)
1 75 4.8 4.4 75 4.7 4.4
3 194 11 4.4 197 10 4.4
7 312 11 4.4 322 6.2 4.4
21 350 0.5 4.5 360 2.4 4.5
42 422 35 4.7 428 31 4.5
63 433 13 4.9 444 14 4.7
Humus 3
(ml/g) (ml/g)
1 57 1.3 6.3 58 1.2 6.3
3 94 4.3 6.4 96 4.0 6.4
7 151 2.2 6.5 153 3.1 6.7
21 321 27 6.6 326 28 6.7
42 465 121 7.1 474 124 7.3
63 785 65 7.0 821 85 7.2
148

APPENDIX 10. Kd values of technetium
Appendix 10.1. Kd values of technetium for the soil layers of the excavator pits OL-KK14, OL-KK15 and OL-KK16.

Soil
(cm) (cm) (cm)
humus 5 15.1 13 5.0 7 126 105 4.6 10 1.44 1.4 6.1
MS1 20 0.20 0.4 5.7 50 -0.09 6.8 7.0 30 0.45 0.7 7.4
MS2 60 0.63 0.6 6.9 80 1.02 0.4 7.5 50 0.80 0.5 7.6
MS3 105 0.62 0.5 7.1 110 0.40 0.3 8.1 110 0.93 0.3 8.1
148
MS4 240 0.54 0.6 7.6 160 0.36 0.9 8.1 300 1.80 0.9 8.2
MS5 - - - - 260 -1.06 3.1 8.8 - - - -
- sample not taken
149

Appendix 10.2. Kd values of technetium for the excavator pits OL-KK20 aerobic and anaerobic and OL-KK21 anaerobic soil samples.
Soil OL-KK20 OL-KK21
depth aerobic anaerobic anaerobic
(m) Geometric Geometric Geometric
Soil
Kd standard Kd standard Eh Kd standard Eh
pH pH depth pH
(ml/g) deviation (ml/g) deviation (RmV) (ml/g) deviation (RmV)
(m)
0.7 1.38 0.8 7.7 2.19 1.4 8.7 367 0.4 42.7 38 7.2 84
1.3 1.27 1.2 8.1 3.04 2.4 9.1 260 1.1 1.05 0.7 8.1 134
2.05 1.45 1.2 8.1 1.10 1.0 9.3 226 1.75 39.8 14 8.8 108
3.0 1.27 0.3 8.0 0.86 0.7 9.4 203 2.4 554 54 8.6 116
3.4 1.22 1.1 8.0 2.62 0.7 9.2 213 2.95 101 82 8.9 46
149
- - - - - - - 3.6 568 166 8.8 73

- sample not taken
150

Appendix 10.3. Kd values of technetium for the excavator pit OL-KK21 untreated and
untreated, irradiated humus samples 1, 2 and 3.
Time Humus 1
(days) Standard deviation
Kd (ml/g) pH
(ml/g)
7 3.54 0.5 7.0
31 366 38 7.7
93 547 39 7.2
Humus 1 Humus 2 Humus 3
Time Standard Standard Standard
Kd Kd Kd
(days) deviation pH deviation pH deviation pH
7 1.82 0.3 5.4 4.46 4.7 4.8 2.38 0.1 5.7
93 8.82 0.4 5.4 12.3 0.3 4.7 7.39 1.4 5.5

Distribution Coefficients of Caesium, Chlorine, Iodine, Niobium, Selenium and Technetium On Olkiluoto Soils

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Distribution Coefficients of Caesium, Chlorine, Iodine, Niobium, Selenium and Technetium On Olkiluoto Soils

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Working Report 2013-68

Distribution Coefficients of Caesium,

Ilkka Välimaa, Martti Hakanen, Jukka Lehto

Saanio & Riekkola Oy

Working Reports contain information on work in progress

Distribution coefficients of caesium, chlorine, iodine, niobium, selenium

Cesiumin, kloorin, jodin, niobiumin, seleenin ja teknetiumin

4.1 Kd values for caesium ..................................................................................... 51

4.6.4 Untreated humus samples of OL-KK21 .................................................. 96

1.1 Posiva’s sorption experiment programme in HYRL

A research project on the overburden migration of long-lived radionuclides originating

2014 sorption experiments

2016 sorption experiments sorption experiments

1.2 Relevance of radionuclides in sorption studies

1.3 Distribution coefficient Kd

Equation 1. The definition of the distribution coefficient Kd. Cs = concentration of the

the radionuclide. At Kd values ≤0.1 ml/g an element can be considered as mobile as

Figure 1. Olkiluoto Island. Topographic database, National Land Survey, permission

2.1.2 General description of soil sampling

Aerobic soil samples

Anaerobic soil samples

2.2 Characterisation of the soil samples

2.2.1 Chemical characteristics

calculated as a sum of Na, K, Mg and Ca ions extracted by 1 M NH4Ac solution in pH

2.2.2 Geotechnical characteristics

Specific surface area (m /g)

Samples were mainly composed of quartz, potassium feldspar, plagioclase and

2.3 Water samples

The sorption of radionuclides is usually examined in two-component electrolyte

2.3.1 Soil solution sampling and chemical characteristics

0 20 40 60 80 100 120 140 160 180

2.3.2 Soil solution simulant

2.3.3 Electrolyte and buffer solutions

2.3.4 Radioactive tracers

 The separation column was made of 5 ml syringe by inserting seven layers of

3.1.1 Cation and anion analysis

3.1.3 Redox potential measurement

3.1.4 Tracer activity measurement

[4]

3.2 Batch sorption studies

The sorption of radionuclides on different materials is usually examined and estimated

3.2.1 Experiment series programme

Table 10 presents a detailed and descriptive summary of the experimental series

3.2.2 Aerobic soil samples

OL-KK14 OL-KK15 OL-KK16 OL-KK20 OL-KK21

3.2.3 Anaerobic soil samples

the Laboratory of Radiochemistry in the nitrogen gas filled AtmosBagTM. At the

3.2.4 Untreated humus samples

To study if sample drying has an effect on the sorption of radionuclides on humus, an

3.2.5 Irradiated humus samples

4.1 Kd values for caesium

100 1000 10000 100000

<0.063 0.063-0.125 0.125-0.25 0.25-0.50 0.50-1.0 1.0-2.0

4.1.2 Aerobic untreated soil samples of OL-KK20 and OL-KK21

4.1.3 Anaerobic untreated soil samples of OL-KK20

Soil depth (m)

500 1000 1500 2000 2500 3000 3500

4.1.4 Untreated humus samples of OL-KK21

The sorption of caesium on untreated humus samples of OL-KK21 is presented in

Table 12. Kd values, standard deviations and equilibrium pH values of Cs-134 on

4.1.5 Effect of competing cations on the sorption of caesium

The sorption of caesium is restrained in high salinity solutions due to enhanced

2,5 Soil water simulant