Journal of Radioanalytical and Nuclear Chemistry

https://doi.org/10.1007/s10967-021-07953-z

Diffusion of acetic acid, butyric acid, and butanol in compacted

montmorillonite
Takamitsu Ishidera1

Received: 30 April 2021 / Accepted: 13 August 2021

© Akadémiai Kiadó, Budapest, Hungary 2021

Abstract
Effective diffusion coefficients (De) of acetic acid, butyric acid, and butanol in compacted montmorillonite were determined
by through-diffusion experiments and compared with those of iodide and deuterated water. The difference in De values
between acetic acid, butyric acid, and iodide could be attributed to the difference in their self-diffusion coefficient values,
while this was not applicable to the De values determined for butanol and deuterated water. This result suggests that the De
values of iodide can be converted to those of carboxylic acid and utilized for migration analysis of carbon-14 in the safety
assessment of geological disposal.

Keywords  Diffusion · Carbon-14 · Acetic acid · Butyric acid · Butanol · Compacted bentonite

Introduction so the retention of C-14 is scarcely expected in compacted

In the geological disposal of radioactive waste, the safety of
disposal is assessed by the radiation dose to the geosphere.
The radiation dose is evaluated based on the rate of release
of radionuclides from radioactive waste to the biosphere.
The radionuclide release rate is calculated by the radionu-
clide migration analysis in various pathways, including engi-
neered barrier, host rock, and water-conducting fault [1–5].
Carbon-14 (C-14) is one of the radionuclides that will domi-
nantly affect the radiation dose in certain types of radioactive
waste disposal, such as the direct disposal of spent fuels
and disposal of waste containing hulls and ends [2, 4, 6, 7].
Therefore, reliable migration parameters of C-14 need to be
introduced into the radionuclide migration analysis.
Diffusion and sorption are the main migration processes
contributing to the retention of radionuclides in compacted
bentonite, which is a main component of engineered barrier.
C-14 has weak sorption properties on compacted bentonite,
* Takamitsu Ishidera
ishidera.takamitsu@jaea.go.jp
1
Department of Geological Disposal Research, Nuclear
Backend Technology Center, Nuclear Fuel Cycle
Engineering Laboratories, Sector of Nuclear Fuel,
Decommissioning and Waste Management Technology
Development, Japan Atomic Energy Agency, Tokai,
Ibaraki 319‑1194, Japan
bentonite by sorption [7–9]. Accordingly, the diffusivity of
C-14 in compacted bentonite will be a dominant factor in
the control of the release rate of C-14 from the engineered
barrier. Effective diffusion coefficient is used as an input
parameter of radionuclide diffusivity in the radionuclide
migration analysis in compacted bentonite. The effective
diffusion coefficient of C-14 should be evaluated with high
reliability.
With regard to the measurement of effective diffusion
coefficient, the chemical form of C-14 is one of the impor-
tant factors since the diffusivity of radionuclides strongly
depends on their chemical form. The chemical form of C-14
released from hulls has been presumed to be inorganic car-
bon and organics of low molecular weight by Kaneko et al.
[10]. Kaneko et al. [10] reported that both inorganic car-
bon and organics were released from zirconium powder,
used to simulate hulls, when immersed in a NaOH solution
under reducing atmosphere. The identified organics were
formic acid, acetic acid, formaldehyde, methanol, and etha-
nol. However, although the effective diffusion coefficient of
inorganic carbon in compacted bentonite has been widely
reported [11–14], only one previous study has examined
the effective diffusion coefficient of organics in compacted
bentonite [12]. Kato et al. [12] determined the effective
diffusion coefficients of alcohols, aldehydes, and carbox-
ylic acids of molecular weights < 100 by through-diffusion
experiments and found lower effective diffusion coefficients

13
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for carboxylic acids compared to those of alcohols and
aldehydes. However, the measured effective diffusion coef-
ficients for C-14 need to be extended for the reliable deter-
mination of effective diffusion coefficient in the radionuclide
migration analysis in compacted bentonite. Moreover, the
understanding of diffusion properties in compacted bentonite
is required to improve the setting reliability.
In this study, effective diffusion coefficients in compacted
montmorillonite of organics with low molecular weight were
evaluated by through-diffusion experiments. Two types of
carboxylic acid with different molecular weights, acetic
acid and butyric acid, were tested to investigate the effect of
molecular weight on diffusion of carboxylic acid. The dif-
ference in diffusivity between carboxylic acid and alcohol
was evaluated by comparing the diffusive behavior between
butyric acid and butanol, whose molecular structures are
similar to each other, except for the functional group. The
effect of montmorillonite dry density was also investigated
by determining the diffusion properties of acetic acid in
compacted montmorillonite at different dry densities. In
addition to the organics, diffusion experiments using iodide
and deuterated water were performed under the same condi-
tions, to understand the diffusion properties of organics in
comparison with that of iodide and deuterated water.
Experimental design
Materials
Acetic acid sodium salt (ARC0158B, American Radiola-
beled Chemicals, Inc.), butyric acid sodium salt (ARC0191,
American Radiolabeled Chemicals, Inc.), and butanol
(ARC0190, American Radiolabeled Chemicals, Inc.) pur-
chased from Japan Radioisotope Association were used as
organic tracers for diffusion experiments. These tracers were
labeled with C-14. The specific activities were 1.85 × ­1012,
2.04 × ­1012, and 1.85 × ­1012 Bq ­mol−1 for acetic acid sodium
salt, butyric acid sodium salt, and butanol, respectively.
Acetic acid sodium salt and butanol were initially stored in
sterile water, while butyric acid sodium salt was stored in
ethanol.
Table 1  Experimental Organic tracer
conditions (Initial concentration)
Reference tracer
(Initial concentration)
Background electrolyte
Montmorillonite dry density
13
Journal of Radioanalytical and Nuclear Chemistry
Kunipia-F (Kunimine Industry Co. Ltd.) was used as the
montmorillonite sample. Kunipia-F is a Na-type montmo-
rillonite containing 1–2% of quartz and calcite [15]. The
structural formula of Kunipia-F is (­Na0.42K0.008Ca0.068)
(Si3.91Al0.09)(Al1.56Mg0.31Fe3+0.09Fe2+0.01)O10(OH)2. Cation
exchange capacity is 116.5 meq/100 g. Kunipia-F was heated
at 110℃ for a day in an incubator to remove adsorbed water
before measuring the weight.
All reagents used in this study, such as NaCl, NaOH, NaI,
and ­D2O, were analytical grade chemicals (Kanto Chemical
Co., Inc.), unless otherwise noted. Solutions were prepared
by deionized water whose resistivity was > 18 MΩ·cm.
Conditions
The experimental conditions for the diffusion experiments
are summarized in Table 1. Acetic acid, butyric acid, and
butanol labeled with C-14 were used as organic tracers for
the diffusion experiments. Acetic acid and butyric acid,
which are carboxylic acids with different molecular weights,
were used to investigate the effect of molecular weight on
diffusion of carboxylic acid. Butyric acid and butanol, which
have the same molecular structure, except for the functional
group, were selected to investigate the effect of the chemical
form of organic carbon.
In addition to organic tracers, iodide or deuterated water
was used in the diffusion experiments as a reference tracer to
compare the diffusion properties with that of organic tracers.
The reference tracers were selected based on the chemical
form of organic tracers. Iodide was selected as the refer-
ence tracer for acetic acid and butyric acid, which diffuse
as anions in compacted montmorillonite under the experi-
mental condition in this study, while deuterated water was
selected for butanol, which diffuses as electrically neutral
species. The diffusion experiments of reference tracers and
organic tracers were performed in sequence. The diffusion
experiments using the organic tracers were conducted after
the experiments using the reference tracers were completed.
Diffusion experiments using acetic acid and butyric acid
were performed using 0.5 mol ­dm−3 NaCl solution adjusted
to pH 8 by NaOH. The experimental equipment was placed
in a ­N2 glove box to prevent a decrease in pH by dissolu-
tion of carbon dioxide from the atmosphere. Acetic acid and
Acetic acid Butyric acid Butanol
(1.2 × ­10−7 mol ­dm−3) (1.7 × ­10−7 mol ­dm−3) (9.4 × ­10−8 mol ­dm−3)
Iodide Deuterated water
(4.5 × ­10−3 mol ­dm−3) (10 wt.% as HDO)
0.5 mol ­dm−3 NaCl 0.5 mol ­dm−3 NaCl
containing < 0.75%
bronopol
0.8 and 1.4 Mg ­m−3 1.4 Mg ­m−3 1.4 Mg ­m−3
Journal of Radioanalytical and Nuclear Chemistry

butyric acid dissociate to acetate ion and butyrate ion at pH

8, respectively, so the diffusivity of acetate ion or butyrate
ion was measured by these experiments. With regard to the
experiment using butanol, a significant decrease in butanol
concentration was observed in a preliminary experiment
conducted to check the stability of butanol. Consequently,
bronopol (2-bromo-2-nitro-1,3-propanediol), which is a
chemical routinely used for disinfection, was added to the
0.5 mol  ­dm−3 NaCl solution to avoid microbial degrada-
tion of butanol. The concentration of bronopol was adjusted
to < 0.75% by diluting a commercially available bronopol
solution (Biological Industries Ltd., Aquaguard-2 Disinfect-
ant Solution). The experiment using butanol was performed
under atmospheric conditions. The pH of the solution was
not adjusted as the dissociation of butanol is negligible
regardless of pH.
The montmorillonite sample was compacted to a dry
density of 1.4 Mg ­m−3. In addition to this dry density, com-
pacted montmorillonite at a dry density of 0.8 Mg ­m−3 was
used for the experiment using acetic acid to determine the
effect of dry density on diffusion properties. The experi-
ments were performed duplicate for each condition.

Procedure

The setup of the diffusion experiment is shown in Fig. 1a

[16, 17]. The experimental setup consisted of a diffusion
cell, two reservoirs, a peristaltic pump with a flexible tube
(PharMed® BPT) and polytetrafluoroethylene (PTFE) tubes
with an internal diameter of 1 mm. Montmorillonite was
compacted to the cylindrical space with a diameter of 20 mm
and thickness of 10 mm in the diffusion cell. Two types
of filters, a hydrophilic polyvinylidene fluoride membrane
filter with a pore size of 0.22 μm and thickness of 125 μm,
(Durapore®, EMD Millipore) and a porous plastic filter with
a pore size of 70 μm and thickness of 2 mm made from
polypropylene filter plate (Flon industry, F3023-01-70),
were placed on both sides of the compacted montmorillon-
ite, as shown in Fig. 1b. The solution from the reservoirs was
continuously recirculated through the filters in the diffusion
cell to maintain the tracer concentration at the same level as
that in the reservoirs. The volume of solution in the larger
reservoir (denoted as high-concentration reservoir) was 1000
­cm3, while the volume in the smaller reservoir (denoted as
low-concentration reservoir) varied in the range from 24 to
56 ­cm3.
The diffusion cell was immersed in 0.5 mol ­dm−3 NaCl
solution for several hours under low pressure after compac-
tion of the montmorillonite. Then, the two reservoirs and a
peristaltic pump were connected to the cell by PTFE tube, as
shown in Fig. 1a. To complete the saturation of compacted
montmorillonite, 0.5 mol ­dm−3 NaCl solution was circulated
from the reservoirs at least 1 month.
Fig. 1  Schematic illustration of through-diffusion experiments. Lay-
out of experiment (a) and structure of diffusion cell (b) [17]
After saturation of the compacted montmorillonite,
sodium iodide or deuterated water was added to the high-
concentration reservoir. The concentration of iodide in
the high-concentration reservoir was adjusted to approxi-
mately 4.5 × ­10−3 mol  ­dm−3 by adding a small amount of
0.5 mol ­dm−3 NaI solution. As for the addition of deuterated
water, 50 ­cm3 of 0.5 mol ­dm−3 NaCl solution prepared by
­D2O was added to the high-concentration reservoir after the
same volume of 0.5 mol ­dm−3 NaCl solution was removed
from the reservoir. The deuterated water concentration was
10 wt.% as HDO since D ­ 2O was dissociated into HDO by
isotopic exchange at this concentration. Hereafter, the deu-
terated water concentration was denoted as HDO concen-
tration. After the addition of tracer solution, an aliquot of
the solution from the high-concentration reservoir was peri-
odically removed to measure the tracer concentration. The
low-concentration reservoir was periodically replaced with
a new reservoir filled with 0.5 mol ­dm−3 NaCl solution to
maintain the tracer concentration sufficiently lower than that
in the high-concentration reservoir. The tracer concentra-
tion in the solution in the low-concentration reservoir was
measured by obtaining an aliquot of solution in the replaced
low-concentration reservoir. The iodide concentration, in

13

suitably diluted samples, was measured using an inductively
coupled plasma mass spectrometer (ICP-MS; PerkinElmer,
NexION300X) or inductively coupled plasma atomic emis-
sion spectrometer (ICP-AES; Shimadzu Corporation, ICPS-
7500). The deuterated water concentration was measured
using a Fourier transform infrared spectrometer (FT-IR:
Thermo Fisher Scientific, Nicolet 6700) with attenuated total
reflectance spectroscopy [16] after dilution by 0.5 mol ­dm−3
NaCl.
The organic tracer was added to the high-concentration
reservoir after the experiment using the reference tracer was
finished. The experiments using organic tracers were per-
formed using the same procedure as the experiments using
reference tracers. When conducting the experiment using
butanol, the solution containing bronopol was added to the
high-concentration reservoir once every 3 weeks to maintain
sufficient disinfection capability. The activity of C-14 in the
solution sampled from the reservoirs was measured by a
liquid scintillation counter (PerkinElmer, Tri-Carb4910TR)
after mixing with a liquid scintillator (PerkinElmer, Ultima
Gold XR). At the end of the experiment, the compacted
montmorillonite was cut with a thin blade into 0.8 mm-
pitched segments to determine the concentration profile of
organic tracer in the compacted montmorillonite. The seg-
ments were immersed in 1 mol ­dm−3 NaCl solution at a
liquid–solid ratio of approximately 20 ­cm3 ­g−1 and placed
for 1 day with periodical shaking to extract the organic tracer
from the segments. An aliquot of supernatant was obtained
after centrifugation at 3780 g for 10 min. The activity of
C-14 in the supernatant was measured after mixing with a
liquid scintillator.
Analytical method
The effective diffusion coefficient (De) was calculated from
Eq. (1), which was derived from Fick’s first law expressed
in Eq. (2), as follows [18]:
L
De = −J (1)
ΔCp
𝜕Cp
J = −De (2)
𝜕x
where J is the tracer flux, x is the distance from the high-
concentration side boundary of compacted montmorillonite,
Cp is the tracer concentration in pore water of compacted
montmorillonite, L is the thickness of compacted montmo-
rillonite, and ΔCp is the difference in tracer concentration in
pore water between each end of compacted montmorillonite.
In the diffusion experiment used in this study, tracer con-
centration in the pore space of plastic filter placed at each
end of compacted montmorillonite was homogeneous as the
13
Journal of Radioanalytical and Nuclear Chemistry
solution in reservoir was continuously recirculated through
the filter. The tracer concentration in the membrane filter,
which was placed between the plastic filter and compacted
montmorillonite, was also considered to be homogeneous
as the advection in the membrane filter is expected due to
its high permeability. Moreover, the thickness of this mem-
brane filter was 125 μm, which was sufficiently thin com-
pared to the thickness of compacted montmorillonite. Thus,
the concentration gradient in the filter was considered to be
negligible. The Cp at the boundary of membrane filter can
be regarded as the same with the tracer concentration in the
solution in reservoir. Therefore, the Cp at the high-concen-
tration end of compacted montmorillonite was assumed to
be equal to CH, which was the tracer concentration in high-
concentration reservoir. The tracer concentration in low-con-
centration reservoir was maintained at < 3% of that in high-
concentration reservoir by replacing the low-concentration
reservoir with a new one at intervals during the experiment.
This concentration can be regarded to be adequately lower
than that of the high-concentration reservoir. Therefore, the
Cp at the low-concentration end of compacted bentonite was
assumed to be zero. For these reasons, the ΔCp in Eq. (2) was
assumed to be equal to CH.
The tracer flux (J) was calculated from the tracer con-
centration in the replaced low-concentration reservoir. The
tracer concentration in the low-concentration reservoir just
before replacement was known to affect the calculation
of tracer flux [19]. The tracer concentration in compacted
montmorillonite near the low-concentration end increased
with increasing tracer concentration in the low-concentration
reservoir. After reservoir replacement, the tracer concentra-
tion in the low-concentration reservoir rapidly increased due
to the release of tracer from the compacted montmorillonite
by a concentration discontinuity at the boundary. This phe-
nomenon leads to an increase in tracer flux, and results in
the apparent variation of measured flux. To suppress this
variation, the solution volume in the low-concentration
reservoir was varied depending on the interval of reservoir
replacement to match the tracer concentration just before the
solution was replaced.
Rock capacity factor (α) was calculated using the follow-
ing equation:
De
𝛼= (3)
Da
L
Da = −J
ΔCb (4)
where Da is the apparent diffusion coefficient and ΔCb is
the difference in tracer concentration in compacted mont-
morillonite, including pore water, between each end of
the compacted montmorillonite. The concentration profile
Journal of Radioanalytical and Nuclear Chemistry
in compacted montmorillonite obtained at the end of the
experiment was used to calculate L/ΔCb in Eq. (4) by assum-
ing that the tracer concentration in compacted montmoril-
lonite linearly decreases at the steady state of diffusion. The
α values can also be determined from the transient phase of
diffusion. However, these α values include large uncertain-
ties because only a few plots were available for the evalua-
tion of transient phase in this study. The α values with large
uncertainties are not sufficiently valuable for the discussion.
Therefore, no α values were determined from the transient
phase.
Formation factor (FF) is defined using the following
equation [20]:
De
FF =
D0
where D0 is the self-diffusion coefficient of tracer in water.
The D0 for each tracer is presented in Table 2 [21, 22]. The
D0 value is known to be dependent on the ionic strength
of solution. However, D0 values at infinite dilution were
used for Eq. (5) due to near lack of reported values regard-
ing the dependence of D0 on NaCl concentration for the
organic tracers. The D0 value of iodide was 1.855 × ­10−9
­m2 ­s−1 in 0.5  mol  ­dm−3 NaCl solution but 2.045 × ­10−9
­m2 ­s−1 at infinite dilution [23]. The D0 value of deuterated
water slightly decreased from 2.195 × ­10−9 to 2.158 × ­10−9
­m2 ­s−1 in 0.5 mol ­dm−3 NaCl solution [22]. Considering
these reported values, although the D0 of organic tracers is
also considered to decrease to some extent, the decrease is
expected to be small. Therefore, D0 values at infinite dilution
will be applicable for the discussion.
Results
Figure 2 shows the changes of flux (J) and tracer concen-
tration in high-concentration reservoir (CH) with time. The
error bars in each plot show the uncertainty associated with
the analytical method. The experiments were performed in
duplicate under the same conditions. The results for the two
diffusion cells are indicated by the different cell numbers in
the same figure. The observed flux for each cell increased
at the beginning of experiment and became constant after
Table 2  Self-diffusion coefficients of organic and reference tracers in
water [21, 22]
Tracer Acetate ion Butyrate Butanol Iodide Deuter-
ion ated water
(HDO)
D0 (× ­10−9 1.089 0.868 0.560 2.045 2.195
­m2 ­s−1)
a certain period. The constant flux suggests that the diffu-
sion of tracer reached a steady state. The measured CH val-
ues were almost constant during the experimental period,
except for the experiment using butanol. The CH of butanol
gradually decreased probably due to a microbial degrada-
tion. However, the rate of decrease was at less than 1% a
week. Thus, the impact of concentration decrease on J and
CH values was negligible. The average J and CH values were
calculated from the plots at the steady state of diffusion. The
average J and CH values are represented in Fig. 2 as solid
lines for the cells with odd numbers and broken lines for the
cells with even numbers. The range of the line is consistent
with the period used for the calculation of average J and CH
values. The De values were derived from these average J
(5) and CH values based on Eq. (1). The De values for each cell
are given in Tables 3, 4 and 5 together with the FF values
calculated by Eq. (5). The errors presented in Tables 3, 4
and 5 are 1σ. The error of De was derived from the standard
deviations of the average CH and J values, and measurement
uncertainties. The error of FF was derived from the propaga-
tion of the error of De.
Previously De values of iodide have been reported in the
range of 1 × ­10−10 to 1 × ­10−12 ­m2 ­s−1 in compacted bentonite
saturated with a solution of ionic strength > 0.2 at dry densi-
ties from 0.9 to 1.8 Mg ­m−3 [12, 24–28] and De values were
shown to decrease with increases in dry density [25]. The De
values of iodide obtained in this study were also in this range
and decreased when the dry density was increased from 0.8
to 1.4 Mg ­m−3. The De values of HDO can be described as
De = 0.47ε4.3D0 when the diffusional direction is the same as
the direction of montmorillonite compaction [16]. The De
value of HDO in compacted montmorillonite at a dry den-
sity of 1.4 Mg ­m−3 was calculated to be 5.2 × ­10−11 ­m2 ­s−1
according to the above equation. This De value is also com-
parable to those obtained in this study. As for iodide, the De
values obtained by cell 3 and 4 were inconsistent with those
by cell 5 and 6, although the experiments using these cells
were performed under the same conditions. The reason for
this variation was not clear. However, such a variation in the
De value for iodide has been sometimes observed in previous
studies using through-diffusion method [12, 24–28].
The concentration profiles of organic tracers in com-
pacted montmorillonite are shown in Fig.  3. The error
bars in each plot show the uncertainties associated with
the measurements. The concentration profile was obtained
for the samples at a dry density of 1.4 Mg ­m−3. The plots
adjacent to both ends of compacted montmorillonite are not
indicated in the figures as the density of compacted mont-
morillonite near both ends was lower than that inside [29].
In this study, the increase in tracer concentration adjacent
to both ends was observed possibly due to the decrease in
dry density. The gradient of Cb (ΔCb/L) was calculated from
the least square fitting to the plots indicated in Fig. 3. The
13
 Journal of Radioanalytical and Nuclear Chemistry

Fig. 2  Changes in flux (J) and tracer concentration in high-con- butyric acid at a dry density of 1.4 Mg ­m−3 (f), and butanol at a dry
centration reservoir (CH) with time for acetic acid at a dry density density of 1.4 Mg ­m−3 (h). Figures (a, c, e, and g) are the results of
of 0.8  Mg  ­m−3 (b), acetic acid at a dry density of 1.4  Mg  ­m−3 (d), reference tracers for (b, d, f, and h), respectively

13
Journal of Radioanalytical and Nuclear Chemistry

Table 3  Summary of De, FF, Dry density 0.8 Mg ­m−3 1.4 Mg ­m−3

Da, and α values for acetic acid
and iodide Cell 1 Cell 2 Cell 3 Cell 4

Iodide
De ­(m2 ­s−1) (8.4 ± 0.4) × ­10−11 (8.7 ± 0.4) × ­10−11 (4.0 ± 0.3) × ­10−12 (4.4 ± 0.4) × ­10−12
FF (4.1 ± 0.2) × ­10−2 (4.3 ± 0.2) × ­10−2 (1.9 ± 0.2) × ­10−3 (2.1 ± 0.2) × ­10−3
Acetic acid
De ­(m2 ­s−1) (5.0 ± 0.3) × ­10−11 (4.9 ± 0.2) × ­10−11 (2.3 ± 0.1) × ­10−12 (2.6 ± 0.1) × ­10−12
FF (4.6 ± 0.3) × ­10−2 (4.5 ± 0.2) × ­10−2 (2.1 ± 0.1) × ­10−3 (2.4 ± 0.1) × ­10−3
Da ­(m2 ­s−1) – – (1.5 ± 0.1) × ­10−11 (1.5 ± 0.2) × ­10−11
α – – 0.16 ± 0.02 0.17 ± 0.02

The error is 1σ

Table 4  Summary of De, FF, Da, and α values for butyric acid and obtained Da and De values based on Eq. (3). The error of
iodide Da was derived from the standard deviations of the average
Dry density 1.4 Mg ­m−3 J value and the least square fitting of concentration profile
in compacted montmorillonite, and measurement uncertain-
Cell 5 Cell 6
ties. The error of α was derived from the propagation of the
Iodide errors of De and Da.
De ­(m2 ­s−1) (2.0 ± 0.2) × ­10−12 (1.5 ± 0.2) × ­10−12
FF (1.0 ± 0.1) × ­10−3 (7.4 ± 0.8) × ­10−4
Butyric acid
De ­(m2 ­s−1) (8.0 ± 1.6) × ­10−13 (6.2 ± 0.9) × ­10−13 Discussion
FF (9.3 ± 1.9) × ­10−4 (7.1 ± 1.1) × ­10−4
Da ­(m2 ­s−1) (7.0 ± 1.9) × ­10−12 (5.8 ± 1.6) × ­10−12 Diffusion properties of organics in compacted
α 0.12 ± 0.04 0.11 ± 0.03 montmorillonite
The error is 1σ
The De values of organic tracers depended on the dry density
of compacted montmorillonite, molecular weight of organ-
Table 5  Summary of De, FF, Da, and α values for butanol and deuter- ics, and chemical form of organics as presented in Tables 3,
ated water 4 and 5. The difference in De values can be discussed based
Dry density 1.4 Mg ­m−3
on FF and rock capacity factor (α). The FF is related to
the geometric properties of compacted montmorillonite and
Cell 7 Cell 8 expressed using the following equation [20]:
Deuterated water
𝛿
De ­(m2 ­s−1) (1.7 ± 0.2) × ­10−11 (2.0 ± 0.2) × ­10−11 FF = 𝜀 (6)
𝜏2
FF (7.8 ± 1.0) × ­10−3 (9.0 ± 0.9) × ­10−3
Butanol where δ is the constrictivity and τ is the tortuosity. The fac-
De ­(m2 ­s−1) (2.5 ± 0.4) × ­10−12 (3.2 ± 1.1) × ­10−12 tors δ and τ are related to the diffusion path of the tracers
FF (4.5 ± 0.7) × ­10−3 (5.7 ± 1.9) × ­10−3 in compacted montmorillonite. The δ and τ cannot be inde-
Da ­(m2 ­s−1) (5.6 ± 1.1) × ­10−12 (6.9 ± 2.4) × ­10−12 pendently determined by diffusion experiment. The term
α 0.45 ± 0.12 0.46 ± 0.23 δ/τ2 is derived from the experiment. The porosity, ε, can be
calculated using the following equation:
The error is 1σ
𝜌
𝜀=1−
𝜌s (7)
plots adjacent to both ends of compacted montmorillonite
were excluded from the fitting. The results of least square where ρ is the dry density of compacted montmorillonite and
fitting are presented in Fig. 3 as solid lines for the cells with ρs is the solid density of montmorillonite. Assuming that the
odd numbers and broken lines for the cells with even num- solid density of montmorillonite is 2.8 Mg ­m−3 [16, 30], the
bers. The Da was calculated from the ΔCb/L and average J porosity of compacted montmorillonite at a dry density of
values by Eq. (4). The obtained Da and α values are given 1.4 Mg ­m−3 is calculated to be 0.5 based on Eq. (7).
in Tables 3, 4 and 5. The α values were derived from the The α is expressed using the following equation:

13

Fig. 3  Concentration profiles of acetic acid (a), butyric acid (b), and butanol (c) in compacted montmorillonite
𝛼 = 𝜀 + 𝜌Kd
where Kd is the distribution coefficient of tracers on mont-
morillonite. Assuming that the Kd of organic tracers and ref-
erence tracers are negligible, the α is equal to ε according to
Eq. (8). When the Kd of tracers are negligible, the α derived
from diffusion experiment based on Eq. (3) is known to cor-
respond to the fraction of pore space in which the tracer
can diffuse. The α value is lower than the physical porosity
calculated by Eq. (7) when the pore space available for the
tracer diffusion is limited.
As shown in Table 3, the obtained De values of acetic
acid at a dry density of 1.4 Mg ­m−3 were 2.3 × ­10−12 and
2.6 × ­10−12 ­m2 ­s−1. These values are lower than those of
iodide obtained under the same conditions, which were
4.0 × ­10−12 and 4.4 × ­10−12 ­m2 ­s−1. In contrast, the FF val-
ues of acetic acid were similar to those of iodide. This
result indicates that the difference in De values between
acetic acid and iodide is derived from the difference in
self-diffusion coefficient. The diffusion of acetic acid and
iodide are consistent with each other in terms of geomet-
ric properties. The FF values obtained from the experi-
ments using acetic acid at a dry density of 0.8 Mg ­m−3 and
butyric acid at a dry density of 1.4 Mg ­m−3 were also con-
sistent with those of iodide as presented in Tables 3 and
4. These results suggest that the difference in De values of
13
Journal of Radioanalytical and Nuclear Chemistry
these carboxylic acids were caused only by the difference
(8)
in self-diffusion coefficients, regardless of the dry den-
sity of the compacted montmorillonite and the molecular
weight of the carboxylic acid. Thus, although molecular
structure is considerably different between the carboxylic
acid and iodine, the diffusion path of carboxylic acid in
compacted montmorillonite is similar to that of iodide.
The obtained α values of acetic acid and butyric acid
ranged from 0.11 to 0.17. These values were significantly
lower than the porosity of compacted montmorillonite,
0.5, at a dry density of 1.4 Mg ­m−3. The lower α value has
been interpreted as the result of anion exclusion effect [31]
and widely reported for the diffusion of iodide in com-
pacted bentonite [24–26, 32]. Thus, the anion exclusion
effect was found also in the diffusion of carboxylic acid
in compacted montmorillonite. This result supports the
conclusion that the diffusion path of carboxylic acid is
similar to that of iodide.
In contrast to acetic acid and butyric acid, the FF values
for butanol were lower than those of the deuterated water
used as the reference tracer (Table 5). This result indicates
that the difference in De values between butanol and deuter-
ated water was not simply derived from the difference in
self-diffusion coefficient. Another diffusion property should
be considered to explain the inconsistency in FF values
between butanol and deuterated water.
Journal of Radioanalytical and Nuclear Chemistry
The α values of butanol were 0.45 and 0.46, which were
comparable to the porosity of compacted montmorillon-
ite, 0.5, at a dry density of 1.4 Mg ­m−3. This indicates that
butanol was distributed within all the available pore space
in the compacted montmorillonite. Deuterated water also
distributes into all available pore space in compacted mont-
morillonite. Thus, since both butanol and deuterated water
diffuse into all pore space in compacted montmorillonite,
the pore structure itself of the compacted montmorillonite
corresponds to the diffusion paths for these tracers. There-
fore, although porosity (ε) and the geometric properties of
diffusion path (δ/τ2) are the factors affecting the FF value
based on Eq. (6), for butanol and deuterated water these
factors are equivalent.
The reason for the lower FF values of butanol may be
due to the variation in the self-diffusion coefficient near the
montmorillonite surface. The self-diffusion coefficient of
water has been found to decrease near the montmorillonite
surface due to the restriction of water molecule mobility
[33] or the high viscosity of the clay-water system [34]. The
self-diffusion coefficient of butanol will also decrease near
the montmorillonite surface by the same process. The lower
FF values may be caused by the difference in the degree of
decrease in the self-diffusion coefficient near the montmoril-
lonite surface between butanol and deuterated water.
Application to the safety assessment of geological
disposal
The De of radionuclides in compacted bentonite needs to be
determined with high reliability for the safety assessment of
geological disposal. The measured De values under various
conditions are essential for the reliable setting of De. Never-
theless, only a limited number of studies can be found with
regard to the measured De values of organics [12].
In this study, the FF value of carboxylic acid was found
to be in good agreement with that of iodide. This indicates
that the De of carboxylic acid can be calculated from the De
of iodide using their self-diffusion coefficients by the fol-
lowing equation:
Dc0
Dce = DIe (9)
DI0
where DeC is the effective diffusion coefficient of carboxylic
acid, DeI is the effective diffusion coefficient of iodide, D0C
is the self-diffusion coefficient of carboxylic acid in water,
and D0I is the self-diffusion coefficient of iodide in water.
According to a database compilation of measured diffusion
parameters in compacted bentonite [35], 93 measured De
values have been reported by 19 separate studies for iodide
in compacted bentonite, whereas only 11 values, including
the results in this study, have been reported on the De for
carboxylic acid [12]. Based on Eq. (9), the reported, meas-
ured De values of iodide can be utilized for the setting of De
for C-14 of carboxylic acid form as supporting data. This
will greatly increase the confidence in setting reliability of
De for C-14.
Regarding the application of Eq. (9), we note that Eq. (9) is
applicable under the conditions tested in this study. The experi-
ments were performed using acetic acid and butyric acid, so
Eq. (9) will be applicable to carboxylic acid whose molecular
weight is approximately between that of acetic acid and butyric
acid. The applicable dry density of compacted bentonite is
roughly in the range from 0.8 to 1.4 Mg ­m−3 as its partial
montmorillonite density [36], which can be introduced to nor-
malize the difference in montmorillonite content in bentonite.
Conclusion
Effective diffusion coefficients (De) of acetic acid, butyric acid,
and butanol in compacted montmorillonite were evaluated by
through-diffusion experiments. Diffusion properties of these
organics were discussed by comparing the diffusivity of iodide
or deuterated water obtained under the same conditions. The
results of diffusion experiments suggest that the difference
in De values between acetic acid, butyric acid, and iodide is
derived from the difference in self-diffusion coefficient regard-
less of the dry density of the compacted montmorillonite. An
anion exclusion effect, which has previously been reported
for the diffusion of iodide, was also found for these carboxylic
acids. Therefore, the diffusion path of carboxylic acid in com-
pacted montmorillonite is considered similar to iodide. This
result implies that the De values of iodide can be converted
to those of carboxylic acid based on their self-diffusion coef-
ficients. The converted De values can be utilized for the De
setting for migration analysis of C-14 in the safety assessment
of geological disposal. In contrast, the difference in De values
between butanol and deuterated water cannot be explained
only by the difference in self-diffusion coefficient.
Acknowledgements  This study was performed as a part of “Project on
Research and Development of Spent Fuel Direct Disposal as an Alter-
native Disposal Option (2015-2017FY)” funded by the Ministry of
Economy, Trade and Industry of Japan. The author would like to thank
Seiichi Kurosawa, Shunji Ohtsuka, Yoshihide Yamada, Akihiro Suke-
gawa and Yuri Hoshino for technical support with the experiments.
Funding  Funding was provided by Agency for Natural Resources and
Energy.
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