Applied Clay Science 47 (2010) 43–50

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Applied Clay Science

ay

Estimating the corrosion of compacted bentonite by a conceptual model based on

microbial growth dynamics
Masashi Nakano a,⁎, Katsuyuki Kawamura b
a
The University of Tokyo, School of Agriculture and Life Science, 1-1-1 Yayoi, Bunkyo-ku, Tokyo, Japan
b
Tokyo Institute of Technology, Division of Earth and Planetary Science, Tokyo, Japan

a r t i c l e in f o
abstract
Article history:
Received 20 December 2007 The microbial corrosion of compacted bentonite by the dissolution of smectite is biophysically, chemically,
Received in revised form 22 August 2008 and mathematically estimated using an energy conservation law established between Gibbs free energy of
Accepted 26 August 2008 formation ΔGf0 from the elements of smectite and the energy required for the growth and living maintenance
Available online 4 September 2008 requirement of microorganisms. The growth and decay dynamics of microorganisms are described with a
universal Monod-type equation in which the specific growth rate and decay coefficient are given as a
Keywords: function of time considering the rapid development of a population of microorganisms at an initial stage and,
Clay in addition, by introducing the change of a density of colonies and the development of bio- films with time.
Corrosion The solution revealed that the corrosion depth of compacted bentonite depended primarily on the population
Microorganism
density of microorganisms that had initially adhered onto the surface, the maximum thickness of bio-films,
Bio-film
and a population of microorganisms at a stable living stage, although they depended on the speci fic growth
Growth dynamics
and the specific decay rate, the ratio of energy required for maintenance to that required for the growth and
the microbial consumption efficiency of energy to Gibbs free energy of smectite. In conclusion, a mean
population of microorganisms came to the maximum value of an order of 106 to 107 cells/cm3 on the bentonite
surface; the thickness of bio-films was 5–10 μm; and the microbial corrosion depth was estimated to be in the
range of less than 0.2 to 2.0 mm per 105 years in nature, provided the density of smectite was kept to be 1.6
Mg/m3 on the compacted bentonite.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction
In the radioactive and other hazardous waste disposal projects, it is
essential to reveal the microbial corrosion of compacted bentonite
over a long term. This will lead to evaluating the microbial durability
of bentonite barriers. Previous studies have suggested that most
microorganisms live in colonies that construct bio-films on the surface
of various materials and they grow and decay with a metabolism
reaction. In the bio-films, an abundance of metabolite and the remains
of microorganisms co-exist. The diffusion of gas and nutrients occurs
(Benefield and Molz, 1985; James et al., 1995; Wimpenny and
Colasanti, 1997). It is widely noted that microorganisms keep their
activity using energy released from ATP, which they produce by
decomposing substrates by oxidation or reduction (Atkinson and
Mavituna, 1991). They use energy in order to produce the ingredients
required in vivo for growth, for cell functions including movement and
to synthesize various metabolites.
Assuming that certain kinds of microorganisms such as
chemoau- totrophs could utilize bentonite as a substrate, they
probably use
⁎ Corresponding author. Tel.: +81 3441 6167.
E-mail address: nakano27@vesta.ocn.ne.jp (M. Nakano).
energy released from the decomposition of smectite and they
produce ATP and metabolites. The processes performed in the
smectite– microorganism–metabolite systems mean the
transformation of the bond energy of smectite into the bond energy
of products and the increases of entropy in the biological and
chemical reactions as well as in the smectite–microorganism–
metabolite systems. The energy then could be described by Gibbs
free energy of formation from the elements ΔG0 in the reactions and
systems. Therefore,
f the corrosion of compacted bentonite could be
estimated by analyzing the microbial dissolution of smectite based
on the energy conservation law established between the Gibbs free
energy of formation ΔG0 from the elements of smectite and f the
energy required by microorganisms, in combination with the
microbial growth dynamics. The growth and decay dynamics of
microorganisms have been studied using the various types of
logistic models. The underlying principle was to write the
equilibrium equation existing between the growth and the decay
rates (Monod, 1949; Hofbauer and Sigmund, 1988; Murray, 1993).
However, it was necessary to decide the proper values of microbial
parameters and to describe the dynamics of the formation of bio-
films in nature, especially, in extreme depths underground.
The objectives of this paper are (1) to propose an energy
conservation law established between the released energy from
smectite and the microbial energy consumption; (2) to examine the

0169-1317/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2008.08.009
4 M. Nakano, K. Kawamura / Applied Clay Science 47 (2010) 43–50

growth and decay of microorganisms under the formation of bio-

The fourth term on the right-hand side, which means
films using the Monod-type equation, and (3) to estimate the
unavailable energy per unit time of the decomposed smectite, can
magnitude of corrosion depth in various cases with different
be given as follows:
microbial parameters and different populations of microorganisms
adhered initially on the
bentonite surface by assuming some possible values of parameters A EO ¼ ð1−1Þe AðnρBLÞ ð2Þ
with reference to the data obtained from existing culture experiments At B
At
in a bio-reactor and field experiments in bio-leaching.
where ζ is the ratio of the energy used per unit time by microorgan-
2. Model development isms to the Gibbs free energy released from compacted bentonite of
thickness L(0 bζ≤ 1) and it denotes the energy consumption effi-
Energy conservation law ciency of microorganisms.

When microorganisms come from the outside and adhere to the Microbial dynamics
surface of compacted bentonite, it is assumed that they form colonies
and the bio-films that are constructed by the stacks of colonies as On the hypothesis that all microorganisms have the same degree
shown in Fig. 1. If microbial requirements such as water and nutrients of activity in bio-films, the increasing rate of living microorganisms
are assumed to be met and bentonite is assumed to be dissolved by in bio-films is written in accordance with the Monod-type equation
microorganisms in the system, it is possible to consider the as follows: (Monod, 1949).
energy
balance in a system containing bentonite, microorganisms, colonies
and bio-films. .Z
A χ
dxΣ μ−κ Z χ ρ dx 3

The energy conservation law in the system can be written as At 0

M ¼ð
0 Þ M ; ð Þ
follows:
AðnρBLÞ Σ
.Z χ Σ Z χ .Z χ AEO where μ and κ are the specific growth rate and the specific decay
A d
coefficient, respectively.
eB ¼ Eμ ρμ
dx 0
ρþ
x
EEM
ld
þ
met
ρmetdx þ
ð1Þ
At At 0 dt 0 At The growth rate of microorganisms can be given by,
A
.Z χ ρμ dxΣ¼ μ d Z χ Mρ dx ð4Þ
where L is the corrosion depth of compacted bentonite, ρ is
B the A 0 0
density of smectite in compacted bentonite, ρμ, ρM, and ρmet are the t
density of microorganisms increasing by the growth, the density of In the same way, the equation describing the decay rate is introduced
microorganisms living in bio-films, and the density of metabolites, as follows:
respectively. εB is Gibbs free energy of smectite, and Eμ, El, and Emet A
are Gibbs free energy required for the growth, living maintenance, and .Z χ ρ dxΣ κ Z χ ρ dx 5
the production of metabolites, respectively. EO is Gibbs free energy of At 0
κ ¼d0 M ; ð Þ
various chemical products and metabolites not needed by micro-
organisms as well as Gibbs free energy dissipated as heat, ξ is a
where ρκ is the density of microorganisms decreasing by decay.
corrosion factor (0 bξ≤ 1) by which the occurrence of corrosion is
The production rate of metabolites is given by the following
defined when bentonite of L in thickness is partly dissolved by
Luedeking–Piret-type equation
microorganisms, χ is the thickness of bio-films, x is a distance from
.Z Z χ
the surface of compacted bentonite, and t is time. The term on the left- χ d
ρ met dx ¼ τ μ .Z χ ρμ
d þ τM 0 ρM dx; ð6Þ
hand side in Eq. (1) expresses the energy released from compacted dt 0 dt 0
bentonite of thickness L. The first term, second term, and third term
on the right-hand side are the energy used per unit time for growth, Σ dxΣ
life maintenance, and metabolism, respectively. where τμ and τM are constants.
The first term and second term in the right-hand side of Eq. (6)
express the growth-associated and non-growth-associated effects,
respectively.

Corrosion depth

Considering that the density of microorganisms and the density

of colonies as well as the density of metabolites change with their
position in a bio-film, it is convenient to introduce their mean value
over bio-film as follows:

Z χ ρ dx χ ρ
i : μ ; M ;met ;and κ
0
i ¼ d i; ð Þ
7
ðÞ
The non-dimensional mean density MM of the living microorganisms
in bio-films is then obtained from Eq. (3) by applying Eq. (7).

ρM
M exp ΣZ t . μ−κ Σ Σ
ln χ dt 8
M ¼ 0 ¼ A ð
ρ − ð ; ð
0 At
Þ
 M. Nakano, K. Kawamura / Applied Clay Science 47 (2010) 43–50
Fig. 1. Schematic structure of a bio-film. 4
where ρ0 is the initial density of microorganisms, which is equal to
the mean density ρM t¼0 adhered to the bentonite surface when t= 0.
 Using the mean values of each density ρμ, ρM, ρmet, and ρκ and
rearranging Eq. (1) by using Eqs. (2)–(7), the depth L of corrosion is
obtained as follows,
ρ eμ
L¼ 0 d dΛ L; ð9Þ
nρB 1eB
where
Λl Z t .. Σdt
e μΣχ
M
L ¼0 μþ
ð10Þ
M
e
and
el ¼ El þ τMEmet ð11Þ
eμ ¼ Eμ þ τμ Emet ð12Þ
Here, ΛL is called a representative value of the corrosion depth. The
εl means the energy required in connection with living microorgan-
isms, εμ means the energy required in connection with the growth,
and the ratio εl/εμ indicates a ratio of allotment between life and
growth on the total energy consumed by microorganisms, while the
ratio εμ/εB indicates a conversion ratio of the energy required for the
growth of microorganisms to the energy released from smectite.
3. Biological parameters
Ecology of microorganisms and growth-decay parameters
When some microorganisms adhere to the bentonite surfaces at
the beginning by coming from the outside or by activating naturally
in bentonite, it can be presumed from the physical and ecological
viewpoints that the rapid growth of microorganisms will occur,
provided that all conditions are just right for them. The growth will
be equilibrated with decay while the decay of microorganisms will
simultaneously increase and soon reach a constant rate, resulting
in a number of living microorganisms reaching a constant that
constitutes a stable state at the final stage.
The specific growth rate μ is described as follows so that μ has a
small value at the beginning and reaches a constant when the
elapsed time becomes large.
. . ΣΣ
μ ¼ μ max 1−aμ d exp −bμ t 2 ; ð13Þ
where μmax is the maximum value of μ, and aμ and bμ, are constants.
The specific decay coefficient κ is assumed to be zero at the
beginning and reach the maximum value κmax, which is equal to the
value of μmax, at the final stage, because it is assumed that the number
of living microorganisms will be in a stable state after a large elapsed
time. They are also given by:
κ ¼ κmax .1−aκ d exp .−bκ t2 ΣΣ; ð14Þ
where κmax is the maximum values of κ, and aκ and bκ, are constants.
Here, the condition μmax = κmax is assumed and the other restrained
conditions are given as aμ b aκ and bμ N bκ between the constants
given in Eqs. (13) and (14) in order to satisfy the biological living
dynamics mentioned above. The constant aμ, κ indicates the value of
intercept on the vertical axis when t= 0. The intercept becomes
smaller when aμ, κ becomes larger. The constant bμ, κ indicates the
slope of the curves. The curve becomes steeper when bμ,
κ becomes larger. The typical curves of Eqs. (13) and (14) are shown
in
Fig. 2. In previous studies, the intrinsic growth rate which was
defined as (μ − κ) was found to be about 2.5 day− 1 for the
microbial pyrite dissolution by T. ferrooxidans and 1.3 to 3.92 day−1
in sulfur oxidation by T. thiooxidans (MacDonald and Clark, 1970;
Konishi et al., 1990, 1995). The specific decay coefficient κ was
proposed to be 0.02 day−1
Fig. 2. Biological parameters. Broken line: μ, solid lines: κ, dotted lines: χ/χmax when
μmax = κmax = 2.0, aμ = 0.5, aκ = aχ = 1.0, bμ = 4.0, and bκ = bχ = 0.15 (a), 0.06 (b),
0.036 (c). Units of μ and κ are day−1. χ/χmax is a dimensionless quantity.
(Molz et al., 1986). Therefore, the values of μmax and κmax might
be chosen to be 1.0–4.0 day−1 as an accepted value with reference
to these values obtained in batch culture experiments.
Development of colonies and dynamics of bio-films
Microorganisms live by forming colonies on the bentonite surface,
and the thickness of bio-films increases with time, while the
population of microorganisms increases until it becomes stable. If
the thickness χ of a bio-film is assumed to have a certain small value
close to the thickness of colonies at the beginning, χ can be supposed
to be given as follows, assuming that the maximum values will appear
at a certain stable state in which the growth and decay rate are in
equilibrium.
. . ΣΣ
χ ¼ χ max 1:1−aχ d exp −bχ t 2 ; ð15Þ
where aχ and bχ are constants, and bχ is equivalent to bκ assuming
that changes of χ continue to occur during the period in which the
growth and decay dynamics occur. χmax is the maximum value of χ.
The typical curves of Eq. (15) are shown in Fig. 2.
A constant of 1.1 in Eq. (15) is set by assuming that the bio-film
thickness may be initially around the 10% of the maximum
thickness. The values of χmax need to be determined in this
conceptual model, although the previous experiments have shown
a bio-film thickness of 10–100 μm on the surface of glasses and
steels (Rittmann and McCarty, 1980; Benefield and Molz, 1985;
Molz et al., 1986; Tazaki, 2005).
It is assumed that colonies are initially scattered on the bentonite
surface and that they gradually reduce the distances between adjacent
colonies while constructing a stack and forming bio-films. When χ
becomes χmax, it is assumed that a perpendicular density of colonies
will be observed (Keevil and Walker, 1992; Costerton et al., 1994) and
that the number of colonies in the first layer of the colony stacks on
the bentonite plane is proportional to the maximum population of
microorganisms. A perpendicular density of the colony stacks then
might be described as follows:
nk ¼ n .1 þ αe−γk Σ 2 ð16Þ
δ suf
1þ
α
where
nsuf ¼ Pdnmax; ð17Þ
suf
and nk is the number of colonies in the kth layer of stacks, while
subscript suf and superscript max indicate the number of colonies in
the first layer and their maximum value, respectively. γ is a
constant. The constants δ and α is determined so that nk is equal to
nsuf when k = 1. In
 thickness of bio-films and the total number of colonies based on a
principle of the mass equivalence as follows,

χmax dρ0 MMmax ¼ 3:53 × 10−11 d ∑kmax nk ð19Þ

1

4. Numerical solutions

Non-dimensional mean density

Fig. 4 shows the changes of the non-dimensional mean density

MM with time. The biological parameters defined by Eqs. (13)–(15),
which are the specific growth rate μ, the specific decay coefficient κ,
and the non-dimensional thickness of bio-film χ/χmax, were given
using constants μmax, κmax, aμ,κ,χ and bμ,κ,χ that are noted in the
captions of Fig. 4. The μmax of 2.0 days−1 was chosen as a possible
value that is slightly smaller than that obtained in bio-leaching
experiments by Konishi et al. (1990, 1995). Fig. 4(a) shows MM in
range from about 5 to 80 when bκ and bχ have large values in range
from 0.06 to 0.15. Fig. 4
(b) shows MM in range from about 150 to 1200 with bκ and bχ of
0.032–0.05. These values of bκ and bχ have been chosen so that the
density of microorganisms did not exceed 107 at the maximum in bio-
films. Fig. 4 shows that the larger is bκ and bχ, the smaller is MM. In
other ward, the smaller is bκ and bχ, the larger is MM. Moreover, Fig. 4
shows that there exists a certain characteristic time T at which the
living dynamics of microorganisms becomes stable. The characteristic
time T was about 4, 10, and 15 days when bκ was 0.15, 0.05, and 0.036,
respectively. Konishi et al. (1990, 1995) have shown that about 10 days

Fig. 3. Density function of colonies and P-function in a bio-film when α= 1.02, δ=

1.25, γ= 0.5, G = 0.206 × 106, and F = −0.109. (a) Colony density as a function of k.
(b) P- function as a function of ρ0MMmax.

this study, it was supposed that δ=1.25, α=1.02, and γ= 0.5 as a

hypothesis based on the computer simulation results by Costerton et
al. (1994) (see Wimpenny and Colasanti, 1997), resulting in bio-films
keeping a sufficient space required for the diffusion of gas and
nutrients in bio-films as shown in Fig. 3(a). P is a coefficient that
decides the number of colonies in the first layer and it changes with
time. In this model, P would be hypothetically expressed as the
following linear equation of ρ0MMmax as shown in Fig. 3(b) since
MMmax will change with time,

P ¼ Gdρ0MMmax þ F ð18Þ

where G =0.208 × 10 and F = −0.109 were supposed as possible and

6

useful values.
In previous studies, colonies have been assumed to be about 10
μm
in diameter and about 5 μm in thickness with a biomass density of
90 kg/colony-m3 on average (Molz et al., 1986). This model indicates
that a colony includes the microorganisms of 3.53 × 10− 11 g
which corresponds to 35.3 cells if the mass of a microorganism is
assumed to be 10− 12 g/cell on average. The maximumsufnumber nmax of
colonies in the first layer is 106 per 1 cm2 because colonies of 103 are
considered to be arranged on a side of 1 cm.
According to the above model, the distance between colonies, d
·μm,
in the first layer of the colony stacks is approximated with d = 10 ×
P− 0.5 using Eq. (17) on the assumption that the colonies
suf of n1/2 are Fig. 4. Non-dimensional mean densities when μmax = κmax = 2.0, aμ = 0.5, aκ = aχ
arranged on a line of unit length and the distance between = 1.0, and bμ = 4.0. (a) Non-dimensional mean densities (5 b MM b 80) when bκ =
colonies
suf is then given by n− 1/2. The maximum thickness of bχ = 0.06 (a), 0.07 (b), 0.09 (c), and 0.15 (d). (b) Non-dimensional mean
bio-films is given by χ- max=5×kmax, where kmax is the number densities (150 b MM b 1200) when bκ = bχ = 0.032 (e), 0.036 (f), 0.04 (g), and
0.05 (h).
of layers when MM =MMmax. The maximum mean density ρ0MMmax is
combined with the maximum
are required to reach the maximum number of cells in a batch culture
10.5 g-cell/mol-ATP in an anaerobic culture of fermentation systems
of T. ferrooxidans and about 6 to 12 days in the case of T. thiooxidans.
(Stouthamer, 1979). Furthermore, the cell yield of T. ferrooxidants on
pyrite FeS2 was 3.30 × 1014 cells/kg-FeS2 in a batch bio-reactor
Representative value of the corrosion depth
(Konishi et al., 1990). When energy required for the growth was
estimated from the values of those cell yields using the mean mass of a
Fig. 5 shows the representative values of the corrosion depth ΛL
microorganism of 10− 12 g/cell, it was close to 4.06 kJ/g-cell. Assuming
with various microbial parameters and constants by using ΛL/χmax
that this energy could also correspond approximately to energy εμ, it
when εl/εμ is 0.1, 1.0, and 2.0 days− 1. When εl/εμ was 0.01 days− 1, a
was reasonable for εμ to be in the range 3 to 4 kJ/g-cell.
curve of ΛL/χmax was close to that of 0.1 days−1 because the
Therefore, it could be considered that the ratios εl/εμ were in the
contribution of εl/εμ to ΛL/χmax became extremely small in Eq. (10).
range 0.1 to 2.0 days− 1. However, it is considered that
On comparing Fig. 4(a) with Fig. 4(b), ΛL/χmax becomes large when
microorganisms such as chemoautotrophs living deep
bκ and bχ are small and, in comparison of Fig. 4(b) with Fig. 4(c),
underground might use the same amount of energy for growth
ΛL/χmax becomes large when μmax and κmax are large.
and living because it is supposed that they are living in a weak
Here, it is proposed to deal with εl/εμ as a virtual parameter
growth system. It is then possible to choose values close to 1 for
because it is generally impossible to draw a clear distinction between
the ratio εl/εμ.
the values of εl and εμ in most living systems of microorganisms.
Regarding the energy used for the maintenance of living εl,
5. Depth of corrosion over a long term
although there are less data, the previous batch culture experiments
have demonstrated that energy used for the maintenance of living
was assumed to be 2.4–6.1 kJ/g-cell/d for E. coli growing an- The corrosion depth for a long term L has been calculated using
Eq. (9), the colony density function nk that was assumed to be Eqs.
aerobically by glucose because the maintenance coefficients were
assumed to be in the range 0.02 to 0.05 g-glucose/g-cell/h (16) and (17), and P-function shown in Fig. 3(b). The results are
(Atkinson and Mavituna, 1991). On the other hand, the values of 0 summarized in Table 1. In this calculation, εB was assumed to be
−430 kmol-Fe2+/kg-cell/h have been reported for T. ferrooxidants about −15.8 kJ/g of beidelite Na 0.33Al2(OH)2(Al0.33Si3.67O10), which
could be estimated from the Gibbs free energy of formation f ΔG
0
(Rossi, 1990). Assuming that those values might correspond
approximately to energy εl, and assuming that there is no wide from the elements of pyrophyllite Al2(OH)2(Si4O10) and paragonite
difference in the energy used for the maintenance of an individual NaAl2 (OH)2(AlSi3O10) (Robie et al., 1979; Saxena et al., 1993), on
the assumption that the energy used by microorganisms came from
living between the species of micro- organisms, it is then possible
the Gibbs free energy of formation ΔG0 from the elements of
for εl to assume to be the values of 2– 6 kJ/g-cell/d. f
smectite. The smectite density of compacted bentonite was assumed
Regarding energy required for the growth, it could be considered
to be 1.6 Mg/ m3, which could be observed in a sample that MX-80
to be close to 2.91 kJ/g-cell, because the released energy from ATP
was extremely compacted to the dry density of about 2.1 Mg/m3.
was
The energy consumption efficiency ζ to the total energy of smectite
7.3 kcal/mol-ATP on average when ATP changed to ADP (Tinoco et al.,
was given as 0.4, and the corrosion factor ξ was unity indicating
2002). On the other hand, the molar growth yield for ATP was about
that smectite in unit volume was entirely dissolved by
microorganisms.

Fig. 5. Non-dimensional characteristic value of corrosion depth ΛL/χmax when aκ = aχ = 1.0 and bμ = 4.0. The figures show the values of εl/εμ.
Table 1 significantly by a population of microorganisms that initially adhered to
Corrosion depth over a long term when aκ = aχ = 1.0 and bμ = 4.0.
the bentonite surface, while the microbial growth and decay is decided
by various microbial parameters and constants. However, case 3 shows
that the strong self-reproduction and a rather long lifetime yield the
f almost same corrosion depth as that of case 2 beyond the contribution of
small initial population, though the initial population is smaller than
that of case 2. The population of microorganisms reaches into the range
from 106 to 107 cells/cm3 in thin bio-films of 4 to 20 μm in thickness at a
stable state. The thickness of bio-films and the distances between the
colonies in the first layer of stacks are shown as a function of the
maximum values of the mean population ρ0MMmax in Fig. 6. The
corrosion depth could be estimated to be in the range of 2.26 × 10− 3 to
52.6 × 10− 3 μm/year. The constants used in calculations are
summarized in Table 2.

6. Discussion

C ρ0 μ aμ bκ ρ0MM χma L for along term

The Gibbs free energy of smectite is almost completely composed of
a cells/c ma
x
d max x
μm/y mm
enthalpy ΔH0, for example, −5744.2 kJ/mol (−15.6 kJ/g) in Gibbs
m3 ay cells/c μm
s d ear /105
1
s−
2 m3
e ay
n s−
Fig. 6. Distances between colonies (solid line) and thickness of bio-films (broken line).
o
.
× 106 ×
10−3
a)
1 4× 2 0.5 0. 1.89 7.5 5.94 0.6
104 . 00 07 0
0 0
0
2 0.5 0.0 3.24 12. 16.80 1.7
. 00 60 50
0
0
2 0.5 0. 6.36 19. 52.60 5.3
. 00 05 50
0 0
0
2 b)
4× 2 0.5 0.0 1.64 5.0 3.45 0.3
103 . 00 40 0
0
0
2 0.5 0. 2.66 10. 11.80 1.2
. 00 03 30
0 6
0
c)
3 4× 2 0.4 0.0 1.52 4. 3.57 0.4
102 . 00 40 85
5
0
2 0.4 0. 2.76 10. 14.90 1.5
. 00 03 80
5 6
0
d)
4 4× 2 0.3 0. 1.08 4. 2.26 0.2
10 . 92 03 07
5 0
5
a), b), c) and d) correspond to a population in slightly polluted water on the ground
surface, in water under ordinary circumstances, in clean water and in natural habitat
in bentonite, respectively.

In Table 1, the case of No.1 corresponds to a case in which a

population of microorganisms similar to that in slightly polluted
water on the ground surface adheres to the bentonite surface. The
situation is expressed by a large initial population of
microorganisms, an ordinary value of μmax, and a large value of bκ.
The No.2 indicates a case in which a population of microorganisms
similar to that in water under an ordinary circumstance adheres to
the bentonite surface and, moreover, microorganisms have a long
lifetime. The situation is shown by a larger value of bκ than that in
the case of No.1. Number 3 shows a case in which a population that
is identical to that in clean water adheres to the bentonite surface
and, moreover, microorgan- isms have a remarkable self-
reproduction and a very long lifetime. The situation is indicated by
a larger value of μmax and a smaller value of aμ than those in the
cases of Nos.1 and 2. Number 4 shows a case in which
microorganisms are reproduced with a remarkable long life in the
same mode as in nature. The dynamics is expressed by the
extremely large value of μmax and a small value of bκ.
Table 1 show that the magnitude of corrosion depth is affected
Table 2 reached the maximum values. It became about 0.51 in layers
Constants used for calculations. beyond the fourth one. Those vacant spaces were assumed to be
Constant Range estimated Value used Unit suitable for the movement of gas and nutrients in bio-films. The
εl 2.0–6.0 – kJ/g−cell/
day
εμ 3.0–4.0 3.5 kJ/g−cell
εl/εμ 0.1–2.0 1 1/day
μmax, κmax 1.0–4.0 2.0, 2.5, 2.55 1/day
εB 14.7–16.0 15.8 kJ/g
ρB 0.75–2.3 1.6 g/cm3
ζ 0.2–0.4 0.4 –
ξ 0.7–1.0 1 –

free energy of −5819.6 kJ/mol (−15.8 kJ/g) for beidellite.

Therefore, it was assumed that a part of Gibbs free energy released
from smectite might be transformed into heat and dispersed. This
is then considered to be included in E0 in the forth term on the
right-hand side in Eq. (1). In addition, a part of smectite
decomposed could remain in an amorphous body (Chaerun and
Tazali, 2005). The Gibbs free energy of the remainders could be
also considered to be included in E0.
The decomposition of substrates or nutrients by
microorganisms generally requires water and inorganic
compounds as well as organic materials besides oxygen in the
chemical and biological reactions. The metabolites produced by
microorganisms are water and such gases as H 2, CO2, NH3 and CH4
besides the synthesized products required in vivo, for example,
ATP and other compounds composing a living body. The Gibbs free
energy of smectite is retained as the bond energy between elements
in metabolites. The Gibbs free energy of the oxidizing agents and
water as well as gases that are excreted in vivo is less than a few
hundred of kJ per mol, which is rather smaller than that of
smectite. It was then considered that they almost do not contribute
to the balance of Gibbs free energy in most cases in the chemical
and biological reactions. However, if Eq. (1) could be applied to
the chemical and biological reaction processes, these Gibbs free
energy might be considered to be also included in the fourth term
on the right-hand side.
The dynamics of growth and decay are usually described by
following a generalized logistic equation:
dv
¼ λv f ðvÞ −
dt
ð20Þ

where v is a population of microorganisms, λ is the intrinsic

growth rate, i.e., means the specific growth rate under a condition
of inexhaustible nutrients, f(v) is the decay term and t is time
(Hofbauer and Sigmund, 1988; Murray, 1993).
In this paper, f(v) was expressed by a linear function of v,
and the intrinsic growth rate and intrinsic self-limiting
coefficient were given as a function of time to consider the rapid
increases of population in the initial stage, for example, by the
changes of the concentration of nutrients and density of
colonies in the progress of the microbial dynamics. In the
model, it was important to determine the proper value of the
parameters used to reflect the microbial dynamics and estimate
the corrosion depth. The numbers of bacteria are 106 to 107
cells/g in soils and in polluted ground water in nature (Harvey
et al., 1984). It is noteworthy that ρoMMmax in Table 1 had the
same levels. The constants used for determining biological
parameters, which are μmax, aμ and bκ, were then considered to
be relatively acceptable.
The density function of colonies was assumed so that the
number of colonies would rapidly decrease to keep the space
required for the diffusion of gas and nutrients from the outside
into the first layer of colonies or from the first layer to the
outside of bio-films. In the model, the ratio of a vacant space
between colonies to the whole surface area of bentonite was
about 0.20 in the first layer when the population of colonies
maximum thickness of bio-films was about 5 to 10 μm. It means Table 3
that bio-films do not develop to be very thick. When the density Gibbs free energy of several minerals.
function of colonies is considered to change with time, parameter γ
Mineral Δ Not
must be dependent upon time. In this case, however, it was f e
assumed that the density function was independent of time because G
0
the maximum thickness χmax of bio-films was very small.
K
The microbial corrosion depth of compacted bentonite was J
influenced by various factors in a complicated way. When it was /
g
supposed to be, for example, 0.1 for the ratio εl/εμ in the case of εl Pyrophyllite −15.85
smaller than 2 kJ/g-cells/d, the corrosion depth was estimated to Paragonite −15.78
decrease by about 70% relative to the results shown in Table 1. On Anorthite −14.39 Feld
spar
the other hand, when the ratio εl/εμ was supposed to be 2.0, the Albite −14.16 Feld
corrosion depth increased by about 1.3 to 1.7 times that in the spar
Aragonite −11.28 Calc
results. When the energy consumption efficiency ζ was smaller, for ite
example, 0.2, that is, one half of the efficiency used in calculations, Illite −14.2
the corrosion depth was twice that in the results. Vermiculite −14.2
Iron vermiculite −10.4
Fig. 7 shows the changes of corrosion depth with the density of Saponite −14.4
smectite under a condition of the first line of each case in Table 1, Iron saponite −10.3
which was calculated using Eq. (9). The curve of case 3 seems to be Quartz −14.25
nearly equal, although slightly above, to the curve of case 2 because Kaolinite −14.72
Gibbsite −15.52
of the large μmax and the small aμ. When the smectite density of Beidellite −15.83
compacted bentonite is smaller than 1.6 Mg/m3, the corrosion
depth increases because it is in inverse proportion to the smectite
density in Eq. (9). In other words, a high density of smectite led to a
small depth of corrosion. Smectite will change gradually in structural and chemical nature
If the microbial corrosion was defined by the dissolution of about over a long term. When the transformation of smectite to illite
50% of smectite, that is, the corrosion factor ξ= 0.5, the corrosion occurs by diagenesis or when chlorite, vermiculite, saponite and
depth was twice that in the results. Therefore, realistically, and their intergrades as well as interstratifications are produced by
generally speaking, the corrosion depth can be estimated to range hydro- thermal action, the microbial corrosion depth of bentonite
from 0.5 to 2 times the values shown in Table 1. However, the existing may be estimated to be accelerated by about 1.1 and 1.5 times for
microorganisms are assumed to decay fully as a result of changing ferrous-free and ferrous bentonite, respectively. The cause is due to
circumstances, and other kinds of microorganisms will be newly a smaller Gibbs free energy of illite, vermiculite, and other minerals
generated in a new environment at a certain time. The ecological of about −10.3 to
succession will be continued for a long time. Although the period in −14.2 KJ/g than that of beidellite as listed in Table 3 (Tardy and
which a population of microorganisms remains stable is unknown, a Duplay, 1992). It is considered that the acceleration of corrosion
period of stability will occur repeatedly at some interval because of through transformation does not depend on a species of ion adsorbed
new species of microorganisms. On this hypothesis, microbial on smectite.
corrosion depth may range from less than 0.2 to 2.0 mm per
105 years in nature except for unexpected developments. 7.Conclusions
The previous studies have shown that a dissolution rate of
oligoclase (ΔGf 0 = −14.2 KJ/g), which is a major constituent of The microbial corrosion of compacted bentonite could be solved by
granite, was in the order of 10− 14 mol·m− 2·s− 1 in the field (Paces, combining the Monod-type equation applicable to microorganisms
1983) and in the order of 10− 12 mol·m− 2·s− 1 in experiments with an energy conservation law established between the Gibbs free
(Busenberg and Clemency, 1976) on average. If those dissolution energy ΔG0f of smectite and the energy used for the microbial
rates are converted into the depth per unit area by using the dynamics and by introducing the density of colonies and the thickness
chemical composition of albite (NaAlSi3O8), those rates yield a of bio-films. The energy required for the growth was estimated to be 3
range of about 3.2 × 10− 5 to to 4 kJ/g-cell based on the ATP requirement of microorganisms. The
3.2 × 10− 3 μm per year. It is then assumed that the microbial energy required for maintenance was given as a value of 2–6 kJ/g-cell/
corrosion d. The energy released from smectite was estimated as −15.8 kJ/g. The
depth of the compacted bentonite will be perhaps equivalent to or energy consumption efficiency ζ of microorganisms was assumed to
slightly larger than that of granite in nature. be 0.4. The model showed the rapid development of a population of
microorganisms during an initial period of approximately 4 to 15 days
and a stable living period thereafter. The depth of microbial corrosion
was determined mainly by the initial population of microorganisms
adhered to the bentonite surface, the maximum thickness of bio-films,
and the population of microorganisms at a stable living stage. The
thickness of bio-films did not exceed 20 μm. The mean corrosion depth
was estimated to range from less than 0.2 to 5.3 mm/105 years in
nature when the smectite density was 1.6 Mg/m3. The corrosion depth
varied inversely with the smectite density. The possible changes in the
energy used by microorganisms and the energy consumption
efficiency yield results of less than twice the above corrosion depth.
From a comparison with dissolution rates for granite component given
in literature, it can be concluded that the microbial corrosion depth of
the compacted bentonite in a repository could be equivalent to, or
slightly larger than, that of granite in nature. The alteration of smectite
Fig. 7. Changes of corrosion depth with the density of smectite. Curves show the might accelerate microbial corrosion by about 1.1–1.5 times.
changes under a condition of the first line of each case in Table 1.
Acknowledgment
 The authors express their sincere thanks to Prof. Dr. Kazuo Nagai,
Coll. of the Bioscience and Biotechnology, Dept. of Biological
Chemistry, Chubu University at Nagoya for criticizing the draft of this
paper.
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