Diffusion of nonreactive and reactive solutes through fine-grained barrier materials

R. W. GILLHAM,M. J. L. ROBIN,AND D. J. DYTYNYSHYN

Department of Earth Sciences, University of Waterloo, Waterloo, Ont., Canada N2L 3GI
AND
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H. M. JOHNSTON
Soils Section Division, Civil Research Department, Ontario Hydro Research Department, 800 Kipling Avenue,
Toronto, Ont., Canada M8Z 5S4
Received January 3, 1984
Accepted April 23, 1984

In many cases where fine-grained geologic materials are used as barriers to the migration of contaminated fluids, the principal
mechanism of contaminant transport is molecular diffusion. Thus the effective molecular diffusion coefficient is the parameter of
greatest importance when predicting migration rates and contaminant fluxes. Diffusion coefficients were measured for two non-
reactive solutes ( 3 6 ~and
1 3 ~and ) one reactive solute ( 8 5 ~ rin) seven mixtures of bentonite and silica sand ranging from 0 to 100%
bentonite by weight. Tortuosity factors were calculated from the results of the nonreactive diffusion experiments, and retardation
factors for the reactive solute from measured distribution coefficient (Kd), bulk density, and porosity values. The results showed
the diffusive transport of both the reactive and nonreactive solutes to be consistent with a Fickian diffusion equation. For practical
purposes, and at the low values of bulk density used in the experiments, the effective diffusion coefficient of the reactive solute
could be calculated with a reasonable degree of certainty from the measured retardation factor and an estimated value of
tortuosity. The results showed that because of the interaction between the distribution coefficient, bulk density, and porosity, an
increase in clay content beyond about 5-10% did not result in a further reduction of the diffusion coefficient of the reactive
For personal use only.

solute.
Key words: diffusion, adsorption, retardation, tortuosity, clay liners.

Dans de nombreux cas ou des matCriaux gCologiques B grains fins sont utilists comrne barrikre contre la migration de fluides
contaminis, le mecanisme principal de transport des polluants est la diffusion molCculaire. Ainsi, le coefficient effectif de
diffusion molCculaire est le paramktre le plus important dans la prediction des vitesses de migration et des flux de polluant.
Des coefficients de difusion ont CtC mesurCs pour deux solutCs non-rCactifs ( 3 6 ~et 1 3 ~et) un solutC riactif (85Sr) dans sept
mClanges de bentonite et sable de silice, la proportion de bentonite variant de 0 B 100% en poids. Les facteurs de tortuositC
ont CtC calculCs B partir des rksultats des essais de diffusion avec les solutCs non-rkactifs, et les facteurs de retardement pour
le solutC rCactif, B partir des mesures de coefficient de distribution (Kd), de densit6 et de porositk. Les rCsultats ont montrk que
le transport par diffusion, aussi bien pour les solutCs non-rCactifs que pour le solutC rCactif, correspondait B 1'Cquation de diffu-
sion de Fick. A des fins pratiques, et aux faibles valeurs de densit6 utiliskes dans les essais, le coefficient effectif de diffusion
du solutC rCactif pouvait &trecalculC avec une fiabilitC acceptable B partir du facteur de retardement mesurC et d'une valeur
estimCe de la tortuositC. Les rCsultats ont monk6 qu'en raison de l'interaction entre le coefficient de distribution, la densit6
et la porositC, une augmentation de la teneur en argile au deli2 d'environ 5 B 10% ne produisait pas de rkduction additionnelle
du coefficient de diffusion du solute rCactif.
Mots elks: diffusion, adsorption, retardement, tortuositk, membranes en argile.
[Traduit par la revu]
Can. Geotech. J. 21,541-550 (1984)

Introduction barrier. If bentonitic clay is used in the construction of

Fine-grained geological materials are finding in-
creased applications as barrier materials for preventing
the migration of contaminants from waste management
sites into local hydrogeologic regimes. Possible applica-
tions include liners for waste lagoons and landfills, grout
curtains, and barrier materials surrounding buried waste
containers. Geologic barriers may be constructed from
local clay materials; in the event that suitable materials
are not available, they are frequently constructed by
mixing bentonitic clay with local materials. Significant
design characteristics include the hydraulic conductivity
of the barrier material and the rate at which the
contaminants of concern will be transmitted through the
the barrier, the proportion of clay that must be mixed
with the local materials to give the desired transport
characteristics can be a very significant economic factor.
The licensing of waste management facilities generally
requires a prediction of the effect of the facility on the
environment. Where barriers are used as a significant
component of the waste containment design, knowledge
of the rate at which contaminants will migrate through
the barrier is required. This of course requires an
appreciation of the mechanisms of contaminant trans-
port through fine-grained materials and an ability to
predict contaminant fluxes through the barrier.
The recognized mechanisms that affect the transport
 542 CAN. GEOTECH. J. VOL. 21. 1984
of solutes through saturated geologic materials include
transport as a result of the bulk motion of the fluid phase
(advection); dispersive transport caused by velocity
variations about the mean velocity, and by molecular
diffusion; and geochemical retardation processes. Of
these, there is a growing body of evidence to indicate
that in fine-grained geologic materials the principal
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mechanism of solute transport is molecular diffusion
(Desaulniers et al. 1981). In particular, Gillham and
Cherry (1982a, b) show that if the average groundwater
velocity is less than about 1.6 X lO-'Orn/s, then
molecular diffusion would be the dominant transport
mechanism. Assuming a hydraulic gradient of and
a porosity of 0.4, this would correspond to a hydraulic
conductivity in the order of 5 X lo-' m/s. Since natural
clay materials have conductivity values in the range of
about 5 X loW9to 5 X 10-'Om/s, and the hydraulic
conductivity of bentonite is generally less than about
m/s, it is reasonable to expect that the principal
mechanism of contaminant transport through many liner
materials will be molecular diffusion.
This paper describes a series of laboratory experi-
ments that examined the diffusive transport of both
For personal use only.
nonreactive and reactive solutes through sand-bentonite
mixtures. The specific objectives of the study were to
determine the applicability of the existing diffusion
theory for predicting the migration characteristics, and
to examine the effects of changes in the bentonite
content on the migration characteristics.
Theory
The equation describing diffusive transport of a
nonreactive solute in a saturated porous medium is
analogous to Fick's second law and, following Bear
(1972), can be written in one-dimensional form as
where c is the concentration of solute in the solution
phase (M/L~),t is time (T), D is the effective diffusion
coefficient of the solute in the porous medium ( L ~ / T ) ,
and x is the space coordinate (L). Although there are
several empirical forms (Manheim 1970; Lerman 1978),
the effective diffusion coefficient (D) is commonly
related to the free-solution diffusion coefficient (Do) by
where T is the tortuosity of the medium. Bear (1972)
suggests 0.67 as a reasonable value for T in granular
materials, and, from a survey of measured values, Per-
kins and Johnston (1963) suggest that T generally falls
within a rather narrow range, from 0.5 to 0.8.
In the present study, diffusion coefficients were
measured by bringing into contact two half-cells packed
with the soil material, one containing tracer and one
tracer-free. After sufficient time had elapsed for a
diffuse concentration profile to develop, the cells were
separated and sectioned, and the concentration of the
tracer in each section was measured. A solution to [I]
was fitted "by eye" to the resulting data in order to
determine the diffusion coefficient.
Provided the diffusion profile at the time of sectioning
does not extend to the ends of the cells, the medium can
be treated as infinite, in which case the initial and
boundary conditions are
[3a] c(x,O) = co for x < 0, and c(x,O) = 0 for x > 0
and
[3b] c(-m,t)=co, and c(m,t)=O
where co is the initial concentration of solute in the
"tagged" part of the porous medium. Solving [ l ] for
these conditions gives
[4] c/co = 112 erfc (x/2<t)
If the diffusion profile extends to the end of the cell,
another solution must be used. In this case, for a porous
medium of length L, the applicable initial and boundary
conditions are
[5a] c(x,O) = co for 0 < x < xo, and c = 0 forxo < x < L
and
dc
[5b] -=O, at x = O and x = L
dx
The solution to [I.] is then given by (Carslaw and Jaeger
1959)
(T)
x cos rlrx sin rlnxo
(T)
Note that [4] gives the plane through which diffusion
occurs at x = 0, whereas the equivalent plane is situated
at x = xo for [6].
The migration characteristics of solutes that undergo
geochemical reactions in the porous medium can differ
substantially from those of nonreactive solutes and thus
for these solutes, [ l ] is not an appropriate model.
Although there are several types of geochemical pro-
cesses that can influence contaminant migration in geo-
logic materials (Cheny et al. 1983), this study was
restricted to those reactions that can be represented
by a constant partitioning parameter, the distribution
coefficient.
The distribution coefficient ( K d ) is defined as the
concentration of solute in the solid phase divided by the
concentration in the solution phase, and is applicable for
 {AM ET AL. 543

reactions that are instantaneous and reversible and in
which there is a functional relationship between the
solution- and solid-phase concentrations. If the functional
relationship is linear through the origin, then
[7] i;/c = constant = Kd
where i; is the concentration of solute in the solid phase
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measurement of diffusion coefficients for the three
tracers in the sand-bentonite mixtures. These were
compared with values calculated from [lo].
Methods of investigation
Porous media
The porous media (soils) used in this study were seven

(MIM). Under these conditions, a retardation factor (R)
can be defined by
where p is the bulk density of the porous medium
(M/L~)and q is the porosity (L3/L3). It can further be
shown that [ l ] becomes
where D, is the effective diffusion coefficient of the
reactive solute in the porous medium ( L 2 / ~ and
) is
given by
For personal use only.
mixtures of silica sand and bentonite clay. The silica
sand was sieved and particles larger than 63 pm were
retained and washed with deionized water. The
bentonite clay was air-dried and passed through a
62.5 pm mesh. The sand-bentonite mixtures contained
0 , 5 , 10, 15,25,50, and 100% bentonite by oven-dried
weight. The clay used was a sodium bentonite from the
Avonlea mine in Saskatchewan, Canada. A 2:l
solution-to-soil water extract of the clay contained 363,
20.3, 1602, and 2 1 pg /mL of Ca2+, ~ g ~Na2+, + , and
K+ , respectively.
Kd measurements
Distribution coefficients for 8 5 ~were
r determined in
duplicate for all soils. The soil-to-solution ratios used
were close to those of the diffusion experiments. The

It should be noted that [9] and [I ] are identical in form 85Srsolution used was a 1.15 X mol/L solution of
and thus solutions of the equation for the diffusion of strontium chloride. The appropriate amount of this
nonreactive solutes are equally applicable for the solution was added to duplicate 10 g samples of soil and
diffusion of reactive solutes. the mixture was allowed to equilibrate, with frequent
For situations in which the Kd is very large, direct stirring, for a period of 5 days in plastic beakers with
measurement of D, from diffusion cells requires very tight-fitting lids. Removal of a portion of the solution
long equilibration times. Alternatively, the parameters phase from the clay-paste materials was problematic in
of [lo] can all be estimated or measured with a that normal vacuum filtering and squeezing methods
reasonable degree of certainty. It is then apparent that proved to be inadequate. Consequently, soil solution
[lo], when applicable, provides a convenient means of was removed by the filtering-centrifuge device shown
evaluating the effective diffusion coefficient for a schematically in Fig. 1. For the high clay content
retarded species. materials, centrifuging at 11 000 r/min (20 000 G) for
The applicability of the Kd parameter is of course 25 min generally gave about a 2-3 mL sample. One
limited by the underlying assumptions and, because of millilitre of the extracted soil solution was diluted with
its empirical nature, has several other difficulties 4.0mL of deionized water. Three millilitres of the
associated with it. Many of these are discussed in Cherry resulting solution was placed in a gamma radiation
et al. (1983) and in Reardon (1981). Nevertheless, it is counter. The 8 5 ~activity
r obtained was expressed in
generally viewed as a reasonable model for representing counts per minute (cpm) per millilitre of soil solution.
the sorption processes of trace constituents and has been Kd values were then calculated from
applied to a wide range of solutes, including cationic
radionuclides, trace organics, heavy metals, ammonium,
calcium, magnesium, and phosphorous (Cherry et al. where ci is the number of cpm/mL of stock solution
1983). added to the soil initially, c is the number of cpm/mL of
The specific objectives of this study were to examine equilibrium soil solution, V is the volume of " ~ r
the applicability of [ l ] and [9] in materials of high clay solution added, and M is the mass of oven-dried soil
content, to determine if [lo] provides reasonable used.
estimates of the effective diffusion coefficients for
reactive solutes in these types of materials, and to DifSusion experiments
examine the effect of clay content on the effective Each diffusion cell consisted of two Plastipak 50 mL
diffusion coefficient. Chlorine-36 and tritium were used plastic syringes with an inner diameter of 2.65 cm. The
as nonreactive solutes and 85Sr as the reactive solute. syringes were modified by removing the needle fittings
The porous media included mixtures of silica sand and and the ridge around the inner diameter to provide for
bentonitic clay. In general, the procedure involved the easy sample extraction. When assembled, the two
 CAN. GEOTECH. J.
MODIFIED 5 0 m L
DISPOSABLE SYRINGE
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# 5 4 0 FILTER PAPER
2 5 4 c m x 2.22cm
RUBBER O-RING
0.45 m MEMBRANE
FILTL'R
PERFORATED NYLON
PLUG
GLASS SCINTILLATION
VIAL
PLEXIGLAS HOLDER
FIG.1. Centrifugation device used for extracting water from
soil for soluble cation and Kd determinations.
syringes were held together by machine screws passing
through holes drilled in the finger grips. A Plexiglas
plug, 2.0cm long, was placed at each end of the
For personal use only.
diffusion cell, and held in place by stainless steel pins
passing through the syringe barrel. A schematic of an
assembled diffusion cell is given in Fig. 2.
Tracer-free soils were prepared by adding a known
volume of deionized water sufficient to saturate the soil.
Tagged soils were saturated with solutions of either 3H,
3 6 ~ 1or
, 8 5 ~ rThe
. specific activity of the 3~ solution
used was approximately 3.7 x lo5Bq/L (10 pCi/L),
and that of the 36Cl solution was approximately 9.25 X
lo5Bq/L (25 pCi/L). The 85Sr solution used was the
same as that used in the batch tests.
The tagged and tracer-free soil-solution mixtures
were allowed to equilibrate for a minimum of 2 weeks in
parafilm-covered plastic beakers. The soils were mixed
with a spatula periodically to ensure a uniform
distribution of the tracer.
Following equilibration, the moisture content of each
soil was determined by drying small duplicate samples
to a constant weight at 105°C. Half-cells were weighed
and the soil was then packed to achieve as high a bulk
density as possible. care was taken to ensure that the
bulk density was the same for tagged and tracer-free
half-cells of the same soil, and to avoid air bubbles
within the packed soil. Once packed, each half-cell was
reweighed, and the mass of the soil determined.
Problems were encountered when packing the silica
sand in that some solution would seep out between the
plug and syringe wall. Attempts were made to correct
this by using paraffin as a sealant.
The tracer-free and tagged half-cells were then
brought together so that the soil surfaces made complete
contact, and were held in place by bolts passing through
the plastic grips. To reduce moisture loss during the
VOL. 21, 1984
MODIFIED 5 0 rnL
DISPOSABLE SYRINGE PLEXIGLAS PLUG
SOIL
f
STAINLESS STEEL
RETAINING PIN
FIG.2. Schematic of an assembled diffusion cell.
diffusion period, Dow Coming high-vacuum grease was
added to the face of the moulded plastic grip of each
syringe before assembly and the assembled cells were
dipped in molten paraffin wax. After the wax hardened,
the cells were placed horizontally on racks in a
controlled-environment chamber at 22 f 1°C where a
high humidity was maintained by trays of water in the
chamber.
Estimates of the sectioning time (i.e., termination
time of the diffusion experiment) were obtained from [ I ]
using D = 9.1 X l ~ ~ c m for ~ / both
s nonreactive
solutes. The D, values for 85Srwere estimated from [lo]
andsetting7 = 0.67, Do = 1.3 X 10-5cm2/s, q = 0.33,
and using the bulk density values calculated for each soil
and the Kd values obtained from the batch experiments.
The time ( t ) required to obtain c/co = 0.9 at a distance
(x) from the interface equal to 213 of the length of the
half-cell was calculated from [8]. These values gave
diffusion times that were too large, allowing the
diffusion profiles to reach the ends of the cells. It was
therefore necessary to use [6] for the data analysis.
At the end of the diffusion experiment (i.e., at the
termination time) the half-cells were separated. Each
half-cell was then placed in a specially designed jig and
sectioned by removing the pins from the Plexiglas plug
and pushing the plug outward with the aid of a long
threaded bolt. The bolt, turned by hand, extruded
0.254 cm of soil per revolution. About 24 samples were
collected from each half-cell, with the length of each
section being either 0.254 or 0.508 cm.
The soil was sectioned using a stainless steel spatula
run along the surface of the plastic grip. Samples were
put into preweighed 20 mL glass scintillation vials, each
containing 10 mL of water. For soils containing 85Sr, the
vials contained 10 mL of 6 mol/L HC1 instead of water.
Acid extraction was used to release s5Sr from the
exchange sites, and, therefore, concentrations obtained
for 85Sr in the extract were in terms of total 8 5 ~inr the
sample. Expressing the concentration of 85Sr in this
manner is equivalent to expressing it in terms of 85Sr in
solution only because Kd is assumed to be constant.
Two samples from each half-cell were taken to
determine the moisture content. One s a m ~ l was
e taken a
few sections from the contact plane and the other was
taken at the opposite end of the half-cell, adjacent to the
 GILLHAM ET AL. 545

plug. Following equilibration, the supernatant solution

in each glass vial was decanted into a Sorvall poly-
ethylene centrifuge tube and centrifuged at 15 000 r/min
for 20min. Samples containing more than 25%
bentonite usually required an additional decanting and
centrifugation before an appropriate volume of clear
solution could be recovered. After centrifuging, 5 mL of 171
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POROSITY

the supernatant solutions of the two nonreactive tracers

were transferred, along with lOmL of scintillation
cocktail, into glass scintillation vials. The vials were
allowed to cool for a few hours in a Mark I11 Automatic
Liquid Scintillation Counter (Model 68802) and then BULK DENSITY l p l

counted to 10 000 counts.

The "Sr was analysed by transferring 3.0mL of 0
I M 40 60 80 100
I
supernatant solutions to counting tubes and counting to % BENTONITE
10000 counts, using a Nuclear-Chicago automatic FIG. 3. Porosity and bulk density of sand-bentonite
gamma counter (Model 1085). The data for all solutes mixtures versus bentonite content.
were then transformed to counts per minute per gram of
soil, and plotted as a function of distance from the the data for a particular soil and thus the values were
interface. averaged and are plotted as a function of bentonite
content in Fig. 3. The porosity decreased from about
Data reduction 0.34 at 0% bentonite to 0.30 at 5% and then increased to
In order to transform the data into normalized concen- 0.84 at 100% bentonite. The initial decrease can be
For personal use only.

tration profiles, values of co, the initial concentration in attributed to clay-size particles filling the pore space
the tagged half-cell, are required. There are several ways between the sand grains. As the proportion of clay
of obtaining co from the "absolute" concentration profiles. increased, the porosity reached a minimum when all the
The usual and most straightforward way is either directly large pores between the sand grains were occupied by
from the absolute concentrations at the smallest values the clay particles. The porosity increased again as the
of x (if conditions [3a] and [3b] are applicable) or to clay occupied more space than that provided by the large
obtain and double the concentration at the interface. For pores between the sand grains.
a combination of reasons, neither method could be used The bulk density values followed the opposite trend, in-
consistently for all experiments. Most concentration creasing from about 1.64 g/cm3 at 0% bentonite to about
profiles showed enough scatter at low values of x to 1.73 g/cm3 at 5%, and then decreasing to 0.39 g/cm3 at
make direct reading difficult and, in many experiments, 100% bentonite.
diffusion extended to the ends of the diffusion cells, in The results of the 8 5 ~batchr Kd determinations are
which case the first method is not applicable. In addition given in Fig. 4 as a function of bentonite content. The
to the diffusion profile reaching the ends of the cell, the values increased almost linearly with clay content, with
concentration profiles in some diffusion cells were values ranging from 0.29 mL/g at 0% bentonite to
asymmetrical so that neither method was applicable. 20.85 mL/g at 100% bentonite.
Consequently, co was obtained using a mass balance on Included in Fig. 4 are values of plq for the diffusion
the concentration profiles, using the equation cells containing 85Sr and the calculated retardation
factors (R). Equation [8] shows that the retardation
factor is proportional to the distribution coefficient (Kd)
and to the bulk density (p), but inversely proportional to
where n is the total number of sample sections analysed, the porosity (q).Although Kd increased by about 70
no is the number of sections in the tagged half-cells, ci is times as the bentonite content increased from 0 to loo%,
the concentration in the ith section (in cpm/g of soil), the bulk density decreased and the porosity increased.
and giis the number of grams of soil in the ith section. The resulting bulk density to porosity ratios increased
The effective diffusion coefficients were then deter- from about 5.0 at 0% bentonite to about 5.9 at 5%
mined by fitting [6] to the measured profiles. bentonite, then decreased to 0.45 at 100%. The resulting
R values increased sixfold, from about 2.45 at 0%
Results and discussion bentonite to 14.35 at 5% bentonite, and then decreased
Retardation parameters to a value of 10.46 at 100% bentonite.
The porosity and bulk density were determined for six It is interesting to note that in the 5-100% bentonite
diffusion cells of each soil mixture; duplicates for each range, the bulk density to porosity ratio affected the R
of the three tracers. There was very little variability in values to about the same degree as Kd. In fact, an
 546
-
20
DISTRIBUTION COEFFICIENT L K ~ I
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RETARDATON FACTOR I R l
a 0.1 mol/L CaC12 at 25°C (Handbook of Chemistry and
BULK DENSITY/ W R O S I T Y L p / ? )
o 20 40 60 80
% BENTONITE
FIG.4. Strontium-85 distribution coefficients, bulk density
to porosity ratios, and retardation factors versus bentonite
content.
For personal use only.
increase of almost an order of magnitude in Kd was
counterbalanced by the decrease in the bulk density to
porosity ratio. For coarse-grained geological materials,
it is frequently assumed that the bulk density to porosity
ratio varies within relatively narrow limits (two to six).
The above results show that this may not be the case for
repacked fine-textured materials, and variations in the
ratio may have a very significant effect on the retardation
factor.
Diffusion of nonreactive tracers
Tortuosity factors were calculated from the results of
the nonreactive solute diffusion experiments. The data
for some of the diffusion cells were discarded when air
entrapment at the interface was obvious. An example of
a nonreactive diffusion profile is shown in Fig. 5 for
tritium in the 50% bentonite mixture.
The experimental data showed a fair amount of
scatter, particularly in the tagged half-cell, where the
concentrations were higher. This trend was present in all
diffusion cells, and it is difficult to assess whether it is an
indication of the actual variation in concentration or is
the result of the extraction and (or) analysis procedures.
Generally, the data showed a high degree of symmetry
about x = 0, c/co = 0.5, for all nonreactive diffusion
cells.
The diffusion coefficient for each nonreactive
diffusion cell was determined by superimposing several
"calculated diffusion profiles" onto the experimental
data. Calculated profiles were obtained from [I] by
varying the diffusion coefficient. The coefficient giving
the best "eye-fit" of the experimental data was taken as
CAN. GEOTECH. J. VOL. 21, 1984
-
the "experimental" diffusion coefficient. More weight
was placed on the data at positive values of x, where the
scatter was usually less, than on the tagged half-cell side
of the interface. This procedure is illustrated in Fig. 5 for
tritium in the 50% bentonite mixture where a value of
D = 1.1 X lop5cm2/s gives the best fit.
Tortuosity factors were calculated for each nonreactive
diffusion cell as the ratio of the experimental diffusion
coefficient of the solute in the soil (D) to the molecular
diffusion coefficient of the solute in free solution (Do)
(see [2]). The values of Do used were 1.19 X cm2/s
for 3 6 ~ 1which
, is the molecular diffusion coefficient of
Physics 1975) and 2.44 X 1 0 - ~ c m ~ /for s tritium
(Klitzsche et al. 1976).
The values of the experimental diffusion coefficient
and tortuosity factor obtained for each diffusion cell of
the nonreactive solutes are presented in Table 1. In spite
100 of the scatter in the data, the duplicate diffusion
coefficients seldom differed by more than 10%. Thus
Table 1 includes only the mean value of the duplicates.
Because of the moderate insensitivity of the calculated
diffusion profiles to small variations in D, the values of
the experimental diffusion coefficient, and thus of the
tortuosity factors, carry an uncertainty that could be as
high as k 10%.
The tortuosity factors for 3 6 ~ 1first decreased from
0.84 to 0.59 as the clay content increased from 0 to 10%
bentonite and then increased to 0.84 at 100%. The trend
was similar for tritium. This behaviour is expected, if
one views the tortuosity factor as the ratio of the net
distance travelled in the porous medium to the length of
the tortuous pathway followed by the molecules in the
medium. At 0% bentonite, the molecules have to diffuse
around the sand grains through fairly large pores. When
a small amount of clay is added, the clay particles
occupy the space between the sand grains and the length
of the molecular pathway increases. As the clay content
increases further, the effect of the sand grains decreases,
and the path length decreases.
The similarity in the shapes of the measured and
calculated diffusion profiles indicates that the diffusion
of nonreactive solutes in clay materials of the type used
in this study is consistent with the Fickian diffusion
model. The observation that the trends were similar for
the two nonreactive solutes as a function of clay content
indicates that they behaved in a similar manner in the
soil. Therefore, for these experimental conditions,
phenomena such as anion exclusion, anion adsorption,
or the exchange of 3H with bound water in the clay did
not appear to have major effects on the diffusion of the
nonreactive solutes. The fact that the tortuosity factors
were usually lower for 3~ than for 3 6 ~ may
1 be due to the
uncertainty in the free-solution diffusion coefficient
(Do) for tritium.
 GILLHAM ET AL

1.12r

-5 2
D = 1.5 x10 cm /s
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* EXPERIMENTAL RESULTS
CALCULATED PROFILES

-8 -4 0 4 8 12
DISTANCE (cm)
For personal use only.

FIG. 5. Diffusion data for 3~ in the 50% bentonite mixture.

TABLE
1. Experimental diffusion coefficients and tortuosity factors for the nonreacting
solutes 3 6 ~and
1 3~

Chlorine-36 Tritium

Experimental Experimental
diffusion diffusion
coefficient Tortuosity coefficient Tortuosity
Soil cm2/s) factor (low5cmvs) factor

0%* 1.O 0.84 1.7 0.70

5% 0.8 0.67 0.8 0.33
10% 0.7 0.59 0.9 0.36
15% 0.8 0.67 1.O 0.41
25 % 0.8 0.67 1.O 0.41
50% 0.9 0.76 1.1 0.45
100% 1.O 0.84 1.2 0.49
*Percent bentonite in the bentonite - silica sand mixture.

Calculated and experimental strontium-85 diflusion co-
eficients
The tortuosity factors obtained from the 3 6 ~and 1 the
3~ diffusion experiments were used in [lo] to calculate
values of the 8 5 ~diffusion
r coefficient (D,) for each soil.
The other parameters used in [lo] were the measured
porosity and bulk density in the 85Srdiffusion cells, the
average Kd values obtained from the batch tests for each
soil, and a value of 1.3 x cm2/s for the molecular
diffusion coefficient of 8 5 ~ in r free solution. The
tortuosity factors for 36Cland for tritium, the retardation
factors, and the resulting 8 5 ~diffusion
r coefficients are
plotted in Fig. 6 as a function of bentonite content. The
calculated diffusion coefficient (D,) was influenced very
strongly by the retardation factor (R), but somewhat less
by the tortuosity factor. This was expected, since R was
usually higher than 10, making 1/R less than 0.1,
whereas the tortuosity factor was usually higher than 0.3
(see [lo]). It should be noted that the calculated values of
D,carry, through the tortuosity factor, the uncertainties
of the experimental diffusion coefficients of the non-
reactive solutes.
An example of an experimental diffusion profile for
"Sr is given in Fig. 7 for the 25% bentonite mixture.
 548 CAN. GEOTECH. J. VOL. 21, 1984

85Sr for each diffusion cell were obtained as for the

nonreactive solutes by "eye-fitting" calculated curves to
the experimental data. More weight was placed on the
RETARDATION FACTOR I R I
data at positive values of x. The experimental diffusion
coefficient values thus carry an uncertainty of about
5-10% for the same reasons as explained for the
nonreactive solutes. The calculated concentration profile
Can. Geotech. J. Downloaded from www.nrcresearchpress.com by Université Laval Bibliotheque on 10/15/15

judged to give the best fit to the data is given by the

solid line in Fig. 7. Also presented in this figure are the
concentration profiles obtained using each of the two
TORTUOSITY (71 calculated diffusion coefficients (dashed lines).
Figure 8 shows that the experimental and calculated

-
CALCULATED D,
diffusion coefficients behaved in a similar manner with
- FROM 3 6 ~ 1 increasing clay content. In all cases, the diffusion
--- FROM )H
coefficients decreased from high values (greater than 20
40 60 x 10-7cm2/s) at 0% bentonite to a minimum of less
% BENTONITE
than 5 X cm2/s between 5 and 10% bentonite. The
FIG.6. Retardation factors, tortuosity factors, and calculated diffusion coefficients then increased and leveled off
D,values for 8 5 ~versus
r bentonite content. between 50 and 100% bentonite. At 100% bentonite, the
experimental D, value and the D, value calculated from
The same general observations may be made for these the 3 6 ~ tortuosity
1 factors were about 7.0 and 8.0 X
profiles as were made for those of the nonreactive cm2/s, respectively, and about 4.5 X cm2/s
solutes; that is, the scatter was usually more pronounced for the Dscalculated from the 3~ tortuosity factors.
For personal use only.

at the higher concentration values (tagged half-cells), Between 5 and 100% bentonite one would expect the
and the data were usually fairly symmetrical about the diffusion coefficient to decrease as the clay content
point x = 0 , c/co = 0.5 for symmetrical cells. This increased because the cation exchange capacity, and
symmetry is expected since the reaction term is assumed thus the Kd value of the porous material, would increase.
to be a function of neither concentration nor time. However, because of the strong influences of bulk
Experimental values of the diffusion coefficient of density and porosity on the retardation factor, the
-5 2
-"EXPERIMENTAL"DIFFUSION COEFFICIENT : 6.5 x 10 cm /s
--- DIFFUSION COEFFlClEM FROM 3 6 TORTUOSITY
~ ~ : 9.1 x 1c5cm2/s

"r DIFFUSION COEFFICIENT FROM 3~ TORTUOSITY

E X P E R I M E N T A L RESULTS
: 5.3 x 1 6cm2/s
~

-10 -6 -2 2 6 10 14 18 22
DISTANCE ( c m )
FIG.7. Diffusion data for "sr in the 25% bentonite mixture.
 GILLHAM ET AL. 549

factor countered the effect of a ninefold increase in the

distribution coefficient. This could have significant
implications in the optimum design of contaminant
barriers. There appears to be little to be gained by
increasing the clay content above about lo%, in that
minimum values of hydraulic conductivity would also
be reached when the pore spaces between the sand grains
Can. Geotech. J. Downloaded from www.nrcresearchpress.com by Université Laval Bibliotheque on 10/15/15

are filled with clay. This may not be the case in situations
where the barrier material is highly compacted.
The insensitivity of the calculated concentration
profiles to variations in the diffusion coefficient was
such that, in many cases, variations of as much as
twofold still produced profiles giving reasonable fits to
the experimental data. The tortuosity factors obtained
CALCULATED 0. C3'c9 TORTUOSITYI
from the nonreactive solute diffusion experiments, though
variable, were generally close to 0.67, the commonly
assumed value. It therefore appears that, for practical
purposes, using the value 0.67 as a tortuosity factor,
together with the free-solution diffusion coefficient and
the retardation factor, could yield very satisfactory
predictions of the effective diffusion coefficient. It
0
, I
20 40 60 80 100 remains to be shown that this would be the case in highly
% BENTONITE compacted soil materials.
For personal use only.

FIG. 8. Strontium-85 diffusion coefficients: experimental

and calculated using 36Cland 3H tortuosities versus bentonite Acknowledgements
content. The authors wish to acknowledge the support of
Atomic Energy of Canada Limited for this study. The
opposite trend was observed. It would seem that, if a authors are grateful to Dr. W. E. Inniss and Dr. J. C.
maximum s 5 ~ retardation
r (i.e., a minimal diffusion Carlson of the Department of Biology, University of
coefficient) is desired, a mixture containing 5-10% Waterloo, for their assistance in several of the analytical
bentonite would be preferable to either pure sand or a aspects. Finally, the authors wish to thank Stephanie
mixture containing more than 10% bentonite. Improved O'Hannesin, Marilyn Bisgould, and Nadia Bahar for
retardation at higher bentonite contents could only be their help in the preparation of the manuscript.
realized in situations where higher degrees of compac-
tion could be achieved.
BEAR,J. 1972. Dynamics of fluids in porous media. American
Conclusions Elsevier. New York.
The results indicate that diffusive transport of both CARSLAW,H. S., and JAEGER, J. C. 1959. Conduction of heat
nonreactive and reactive solutes in the clays of this study in solids. Clarendon Press, Oxford.
CHERRY,J. A., GILLHAM, R. W., and BARKER, J. F. 1984.
is consistent with the Fickian diffusion equation. The Contaminants in groundwater: chemical processes. In
results further indicate that, for practical purposes, Studies in geophysics. Groundwater contamination. Na-
distribution coefficients ( K d )provide a convenient and tional Academy Press, Washington, DC.
simple means of estimating the reaction tern of the DESAULNIERS, D. E., CHERRY,J. A,, and FRITZ,P. 1981.
diffusion equation for 8 5 ~inr sand-bentonite mixtures. Origin, age and movement of pore water in argillaceous
One would expect a similar behaviour for other solutes Quaternary deposits at four sites in South-Western Ontario.
and soil materials in which the reaction with the porous Journal of Hydrology, 50, pp. 23 1-257.
medium can be described by a distribution coefficient. GILLHAM, R. W., and CHERRY, J. A. 1982a. Predictability of
The results also showed that a small amount of clay solute transport in diffusion controlled hydrogeologic
mixed with sand (5-10% bentonite) was more effective regimes. Proceedings of the Symposium On Low-level Waste
Disposal: Facility Design, Construction and Operating
in retarding 85Sr than either pure silica sand or mixtures Practices, September 28-29, 1982, Washington, DC.
of higher clay content. Within the experimental United States Nuclear Regulatory Commission. In press.
constraints of this study, as the clay content increased 19826. Contaminant transport by groundwater in
from 5 to loo%, even though the soils were packed as non-indurated deposits. I n Recent trends in hydrogeology.
tightly as possible by hand, the effect of increasing Edited by T. N. Narisimhan. Geological Society of
porosity and decreasing bulk density on the retardation America, pp. 3 1-62.
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HANDBOOK OF CHEMISTRY AND PHYSICS.1975. 56th ed. MANHEIM, F. T. 1970. The diffusion of ions in unconsolidated
Edited by R. C. Weast. Chemical Rubber Company Press, sediments. Earth and Planetary Science Letters, 9, pp.
Cleveland. 307-309.
KLITZSCHE,C., WEISTROFFER, K., and ELSHASLY,E. M. PERKINS,T. K., and JOHNSTON, 0. C. 1963. A review of
1976. Grundwasser der Zentralsahara: Fossile Vorrate. diffusion and dispersion in porous media. Society of
Geologische Rundschau, 65, p. 264. Petroleum Engineers Journal, 3, pp. 70-84.
LERMAN, A. 1978. Chemical exchange across sediment water REARDON, E. J. 1981. Kds, can they be used to describe ion
interface. Annual Review of Earth and Planetary Sciences, exchange reactions in contaminant migration. Ground
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