0laboratory Diffusion Testing

Journal of Contaminant Hydrology, 7 ( 199 I) 177-217 177
Elsevier Science Publishers B.V., Amsterdam
Review Paper
Laboratory diffusion testing for waste d i s p o s a l -

A review
Charles D. Shackelford
Department of Civil Engineering, Colorado State University, Fort Collins, CO 80523, U.S.A.
(Received October 25, 1989; revised and accepted September 12, 1990)
ABSTRACT
Shackelford, C.D., 1991. Laboratory diffusion testing for waste disposal - - A review. J,
Contain. Hydrol., 7: 177-217.
This paper reviews the state-of-the-art for the measurement in the laboratory of diffusion
coefficients of chemical waste constituents in fine-grained soils. The purpose of the review is to
present the experimental and analytical methods for determining liquid-phase diffusion coeffi-
cients which can be used in practice for the design and evaluation of waste containment
barriers.
After the appropriate equations describing mass transport in soil are presented, the practical
significance of diffusion coefficients in soil (known as "effective diffusion coefficients") are
described. Appropriate analytical solutions required to calculate the effective diffusion coeffi-
cient (D*) from the measured laboratory data also are presented for several different initial and
boundary conditions. The advantages and disadvantages of each method are noted.
A summary of effective diffusion coefficients from the literature suggests that the major
physical factor affecting the value of the measured diffusion coefficient is the degree of
saturation of the soil, with D*-values for nonreactive and reactive solutes in saturated soils
being as much as 10-20 times higher than the corresponding values in unsaturated soils. Most
of the other physical factors only become important in soils which are highly unsaturated. In
addition, the diffusive transport rates of reactive solutes subject to reversible sorption reactions
can be as much as 5000 times lower than those of nonreactive solutes in saturated soils and from
20 to 630,000 times lower in unsaturated soils.
INTRODUCTION
T h e r e s u l t s o f r e c e n t f i e l d s t u d i e s i n d i c a t e t h a t d i f f u s i o n is a n i m p o r t a n t , i f n o t
d o m i n a n t , t r a n s p o r t p r o c e s s i n f i n e - g r a i n e d s o i l s (e.g., G o o d a l l a n d Q u i g l e y ,
* This paper was first presented at the session on "Clays as Containment Barriers" at the 26th Annual
Meeting of the Clay Minerals Society, California State University, Sacramento, California, U.S.A.,
September 25-28, 1989.
0169-7722/91/$03.50 © 1991 - - Elsevier Science Publishers B.V.

178 C.D. SHACKELFORD
NOTATION
List of symbols
A cross-sectional area of soil

C mass concentration of solute based on volume of solution in soil
C' mass concentration of solute based on total volume of soil
co initial mass concentration of solute in source solution
Ct mass concentration of solute in source solution at time t
CT,m total, measured mass concentration of mobile (adsorbed plus liquid phase) chemical
species based on volume of solution in soil
C total mass concentration (adsorbed plus liquid phase) of the chemical species based
on the total volume of soil
D ~ effective diffusion coefficient
DZ apparent (effective) diffusion coefficient
Oh hydrodynamic dispersion coefficient
n~ mechanical dispersion coefficient
Do free-solution (aqueous) diffusion coefficient
n~ effective diffusion coefficient of reactive solute
erf(z) error function of argument z
erfc(z) complementary error function of argument z
U~ height of source solution
J mass flux vector
J, diffusive mass flux
L straight-line, macroscopic distance between two points in soil
L~ actual, microscopic or effective distance between two points in soil
m mass of solute; also, constant in summation series
m 1, m 2 . mass of solute
io initial mass of solute in soil or in source reservoir
i~ mass of solute in soil after time t
M~ mass of solute in soil at infinite time; equilibrium mass of solute in soil
n total porosity of soil
ne effective porosity of soil
qm non-zero positive root
Q, mass of diffusing solute per cross-sectional area of soil at time t
R general term representing chemical and/or biological reactions
R~ retardation factor
St degree of saturation of soil
t time
tl/2 half-life of radioactive tracer
T~ diffusive time lag
Us seepage velocity
X direction of transport
Z argument for erf or erfc
V vector gradient operator
coefficient in analytical solution
A difference operator
), rate constant
T tortuosity factor, (L/Le) 2
LABORATORY DIFFUSION TESTING FOR WASTE DISPOSAL A REVIEW 179
1977; Desaulniers et al., 1981, 1982, 1984, 1986; Crooks and Quigley, 1984;
Johnson et al., 1989). These findings can have a significant effect on the design
of waste containment facilities since it usually is assumed that advection, not
diffusion, governs the transport of contaminants through earthen barriers. As
a result, laboratory diffusion testing will become a necessary component of the
overall design and evaluation processes associated with waste disposal
practice.
After the equations governing the transport of contaminants through
porous media are reviewed, the practical significance of diffusion in waste
disposal is discussed. Then laboratory methods which can be used to measure
liquid-phase diffusion coefficients of chemical species diffusing through fine-
grained soils used as waste containment barriers are presented. The
laboratory methods reviewed are based on the assumption that the soil is a
continuum. Several additional considerations in laboratory diffusion testing
are discussed after presentation of the methods.
TRANSPORT EQUATIONS
Flux equations
The mass flux of a chemical species (solute) in a saturated soil under the
combined effects of hydraulic and concentration gradients for one-dimension-
al transport is given by (see the Notation for symbols used in this paper):
J = n(v se - Dh'Oe/ax) (1)
where J is the mass flux [M L -2 T-~]*; n is the total porosity of the soil
(dimensionless); vs is the seepage velocity of the fluid (solvent), usually water
[L T- ~]; c is the mass concentration of the solute in the liquid phase of the soil
[M L-3]; x is the direction of transport [L]; and Dh is the hydrodynamic
dispersion coefficient [L 2 T ~]. The hydrodynamic dispersion coefficient
accounts for both mechanical dispersion and diffusive dispersion of the solute
during transport and can be represented by:
Dh = D m + Doz (2)
where Dm is the mechanical dispersion coefficient [L 2 T I]; D o is the free-solu-
tion (aqueous) diffusion coefficient of the solute [L2 T-~]; and z is the dimen-
sionless tortuosity factor. Values of D o for most c o m m o n inorganic chemical
species typically range between ~ 7" 10- to to ,-~ 2.0" 10-9 m 2s- I (Shackelford
and Daniel, 199 la). The mechanical dispersion coefficient is a function of the
* M, L and T in brackets [ ] designate dimensions where M is mass, L is length and T is time.

magnitude of vs and accounts for spreading of the solute during transport due
to variations in the seepage velocity (Freeze and Cherry, 1979).
The tortuosity factor, ~, is purely geometric and accounts for the increased
distance of transport and the more tortuous pathways experienced by solutes
migrating through soil. It usually is expressed as follows (Porter et al., 1960;
Olsen and Kemper, 1968; Bear, 1972):
r -=- ( L / L e ) 2 (3)
where L is the straight-line, macroscopic distance between two points defining

the flow path, and Le is the actual, microscopic or effective distance of flow
through the soil between the same two points. Since Le > L for porous media,
r < 1. Values of ~ are reported to be in the range from 0.01 to 0.84 for
saturated soils and from 0.025 to 0.57 for unsaturated soils (Shackelford and
Daniel, 1991a). In some cases, the tortuosity factor has been defined as the
reciprocal of eq. 3 and, therefore, will have a value greater than unity (e.g.,
Wyllie and Spangler, 1952; Bear, 1972; Li and Gregory, 1974).
For typical problems involving low-permeability earthen barriers used for
waste containment facilities, mechanical dispersion does not appear to be
significant, i.e. Dh ~ D* (Rowe, 1987). In such cases, the total solute flux,
assuming coupled flow processes are negligible, becomes:
J = n(v~c - D or'Sc/Sx) (4)
When there is only a concentration gradient, vs and, therefore, Dm are zero
and eqs. 1 and 4 reduce to the following form of Fick's first law for one-dimen-
sional diffusive transport in saturated soil:
JD ~- --Dorn'Sc/Sx (5)
where JD designates the diffusive flux.
Effective diffusion coefficients
There currently are no satisfactory methods for determining independently

the tortuosity factor, ~. This problem is circumvented by defining an effective
diffusion coefficient, D*, which includes the effect of tortuosity, or:
D* = D0r (6)
When eq. 6 is utilized, the expression for Fick's first law for diffusion in a
saturated soil (eq. 5) becomes:
JD = --D*n'Oc/Ox (7)
Several other forms of Fick's law for diffusion in soil have been suggested
(e.g., Shackelford and Daniel, 1991a). The most common alternate form of
L A B O R A T O R Y D I F F U S I O N TESTING F O R WASTE DISPOSAL A REVIEW 181
Fick's first law is as follows:

JD = --D*'Oc/Ox (8)
where the definition for D* includes the porosity, n (i.e. D* = Dovn ).
However, since the porosity, n, of the soil usually can be determined indepen-
dently, the definition for D* given by eq. 6 and the expression for Fick's first
law given by eq. 7 is assumed to apply in this paper.
Transient equations
The transient transport of a chemical species through a representative

volume of a saturated soil is given by the continuity equation, or (e.g., Bear
and Verruijt, 1987):
~C/Ot - V'J -t- R -t- 2 C (9)
where C is the total mass concentration (adsorbed plus liquid phase) of the
chemical species based on the total volume (solids plus voids) of soil [M L-~];
2 is a rate constant [T -~ ] used to describe such reactions as radioactive and/or
biological decay; and R is a general term representing all other chemical and
biological reactions [M L -3 T-~]. The positive signs ( + ) in eq. 9 are used for
concentration source terms (e.g., mineral dissolution) whereas the ( - ) signs
are used for terms representing concentration sinks (e.g., precipitation).
For many practical applications involving transport of contaminants
through relatively thin, low-permeability materials (e.g., fine-grained soil
barriers), the material is assumed as homogeneous, isotropic and non-
deformable, and transport is assumed to be governed by steady flow of an
incompressible fluid. In addition, only linearly reversible sorption reactions
typically are included in modeling contaminant transport through fine-
grained porous media (i.e. R = 0), and coupled flow process are neglected. If
these assumptions are acceptable, eq. 9 reduces to the advection-dispersion
equation which, for one dimension (say, the x-direction) can be written as
follows (e.g., Freeze and Cherry, 1979):
3e/Ot = (Dh/Rd)'~?2c/Ox 2 -- (vs/Rd)'Ocfi?x (10)
where R d is the dimensionless retardation factor. The retardation factor
represents the relative rate of transport of a nonreactive (nonadsorbed) solute
(e.g., C1-) to that of a reactive solute subject to reversible sorption or equi-
librium exchange reactions (Freeze and Cherry, 1979). For nonreactive (non-
adsorbing) solutes, Ra = 1.
When the seepage velocity is sufficiently low such that mechanical
dispersion is negligible, the advection-dispersion equation (eq. 10) effectively
reduces to an "advection-diffusion" equation, or:
~c/~t = (D*/Rd)'O2c/Ox 2 - (vs/Rd)'dc/Ox (11)

For radioactive tracers, the decay term, 2C, in eq. 9 should be evaluated.
The decay term usually can be neglected if the half-life, ill2, of the radioisotope
is long relative to the time frame of the study. However, if the half-life is short
relative to the time frame of the study, the decay term should be included in
the formulation of the transport equations (e.g., Patil et al., 1963). For linear
or first-order decay, the decay constant assumes the following form (de
Marsily, 1986):
2 = ln(2)/fi/2 = 0.693/tl/2 (12)
Radioactive tracers with long half-lives typically are selected for laboratory
diffusion studies so that the decay term can be neglected without incurring
significant error in the test results.
F i c k ' s s e c o n d law
As the seepage velocity is reduced, diffusion becomes more significant

relative to advection. In the limit, the seepage velocity approaches zero, and
eqs. 10 and 11 reduce to the following expression for Fick's second law for
diffusion of solutes in soil:
Oc/Ot = (D*/Rd)'O2c/Ox 2 (13)
TABLE 1
F o r m s o f F i c k ' s s e c o n d l a w for d i f f u s i o n in a s a t u r a t e d soil
D e f i n i t i o n o f D* Definition of Adsorption Form of Fick's

concentration second law
D oz c no ~c/~t = D * . 0 2c/~x 2
c' no Oc'/Ot = D*'O2c'/Ox 2
c yes c~c/Ot = (D*/Rd).~2c/#x 2
c' yes ~c'/~t = (D*/Rd)'t~2c'/~x 2
D ozn c no Oc/Ot = (D*/n)'O 2c/Ox 2
c' no Oc'/Ot = (D*/n)'~2c'/~x 2
c yes Oc/Ot = (D*/nRo)'O 2c/ox 2
c' yes Oc'/Ot = (D*/nRd)'O2 c'/Ox 2
c = m a s s c o n c e n t r a t i o n o f s o l u t e b a s e d o n v o l u m e o f s o l u t i o n in soil; c' = m a s s c o n c e n t r a t i o n
o f s o l u t e b a s e d o n t o t a l v o l u m e o f soil ( = nc); D * = effective d i f f u s i o n coefficient; Do = free-
s o l u t i o n ( a q u e o u s ) d i f f u s i o n coefficient; n = t o t a l p o r o s i t y o f soil; t = t i m e ; x = d i r e c t i o n o f
transport; z = tortuosity factor.
L A B O R A T O R Y D I F F U S I O N TESTING F O R WASTE D I S P O S A L - - A REVIEW 183
Several other expressions for Fick's second law of diffusion, summarized in

Table 1, exist due to differences in: (1) the definitions of D*; (2) the reference
frame for the expression of the solute concentration; and (3) the behavior of
the adsorbing solutes during transport relative to that of the nonadsorbing
solutes. These differences in the formulation of Fick's second law should be
noted carefully since failure to account for them can affect conclusions drawn
from test results and/or model studies.
Of particular interest is the ratio D*/Rd which appears as a coefficient terms
in eqs. 11 and 12. In some cases (e.g., Li and Gregory, 1974; Gillham et al.,
1984; Quigley et al., 1987), this ratio has been combined into a single coeffi-
cient as follows:
#c/Ot= D*'OZc/ax 2 = Ds'O2c/Ox 2 (14)
where
= Ds = D*/Sd (15)
and D* is known as the "apparent diffusion coefficient" whereas Ds is known

as "the effective diffusion coefficient of the reactive solute". The result of this
substitution is that only one unknown (D* or Ds) must be determined from
test results instead of two unknowns (D* and Rd).
The coefficient D* or Ds is a function of the sorption characteristics of the
soil, whereas D* is not. Therefore, since different soils have different sorption
characteristics, it is meaningless to report a value for D~ or Ds without
reporting the associated Rd-value. Also, an error in interpretation on the
order of Rd-1 can result if the difference between D*- or Ds-values and
D*-values is not recognized (Shackelford and Daniel, 1991a).
Types of diffusion coefficients
There are essentially four different types of diffusion (Robinson and Stokes,
1959; Li and Gregory, 1974; Shackelford, 1988a, 1989; Shackelford and
Daniel, 1991 a): (1) self-diffusion; (2) tracer diffusion; (3) salt diffusion; and (4)
counter-diffusion or interdiffusion. However, the objective of most waste
disposal or containment situations is to isolate potential contaminants from
groundwater supplies. With respect to laboratory test conditions, this
situation is analogous to the salt diffusion system. In a salt diffusion system,
one half-cell is tagged with a salt solution (e.g., a NaC1 solution) whereas a
separate half-cell contains only the solvent (e.g., water). When the two half-
cells are connected, diffusion of the solutes (e.g., Na + and C1-) occurs from
the tagged half-cell to the untagged half-cell until the concentration of the
solutes in both half-cells is equal, and the system is in equilibrium.
Two practical examples of salt diffusion systems related to waste disposal
Clay Liner
Aquifer
(a)
Slurry Wall
Ground Surface ~ C 1 ) C2
w.r.~r_ I w.'r. , v
C1 " - - ~ C2
Waste Containment
Area
(b)
Fig. 1. Examples of diffusive transport through clay barriers: (a) clay liner and (b) slurry wall containment
(after Gray and Weber, 1984).
or containment are illustrated in Fig. 1. In these cases, the concentrations of

the contaminants on the containment side of the barrier typically are higher
than the corresponding concentrations on the opposite side of the barrier. As
a result, a concentration gradient is established across the barrier, and the
contaminants diffuse from the containment side of the barrier to the opposite
side of the barrier.
Significance of diffusion in waste disposal
As a result of the above considerations, it is of interest to evaluate when

diffusion dominates the transport process. Rowe (1987) concluded that
mechanical dispersion was insignificant relative to diffusion for typical
LABORATORY DIFFUSION TESTING FOR WASTE DISPOSAL--A REVIEW 185
problems involving earthen barriers when the fluid flow flux or Darcian
velocity is ~<0.1m yr -1. Gillham et al. (1984) indicate diffusion is dominant
when Vsis on the order of 0.005 m yr -~ . For a clay liner, this seepage velocity
corresponds to a saturated hydraulic conductivity of 8- 10-l~m s-~ when the
porosity of the soil is 0.5 and the hydraulic gradient is one. Since current
regulations in the U.S.A. require the saturated hydraulic conductivity of
certain clay liners to be ~< 1 • 10-9m s -I, it is evident that diffusion could be a
significant, if not dominant, transport process in many waste disposal
situations. Also, in the absence of coupled flow processes, the best contain-
ment barrier that can be built is one in which diffusion controls the transport
of the contaminants (Daniel and Shackelford, 1988; Shackelford, 1988b).
Therefore, the need for measuring effective diffusion coefficients of contami-
nants in fine-grained soils is apparent.
METHODS OF MEASUREMENT
In general, methods used to measure effective diffusion coefficients of

chemical species fall into two broad categories, steady state and transient,
corresponding to the type of transport equation used in the analysis for the
determination of the D*-values. This section presents some of the more
c o m m o n procedures which have been used to measure effective diffusion coef-
ficients.
The steady-state method
The steady-state method for determining D*-values has been used by

Husted and Low (1954), Dutt and Low (1962), Olsen et al. (1965), van Schaik
and Kemper (1966), van Schaik et al. (1966), Tinker (1969), and Muurinen
(1990), among others. A schematic diagram illustrating the steady-state
method is presented in Fig. 4a on p. 191. The soil is contained between two
reservoirs - - a source reservoir containing the solution of interest (e.g., an
actual or simulated leachate) and a collection reservoir from which samples
are withdrawn for chemical analysis of specified chemical species. The concen-
tration of the chemical species of interest is higher in the source reservoir than
it is in the collection reservoir; therefore, a concentration gradient is esta-
blished across the soil sample, and eq. 7 can be utilized for determining D*
once steady-state conditions have been reached, as follows:
D* = - (Ax/nAc)J D = - (L/nAc)(Am/AAt) = - (L/nAAc)(Am/At) (16)
where L and A are the length and cross-sectional area of the soil sample,
respectively; Ac is the concentration gradient; and Am is the change in mass
of the chemical species in an increment of time, At. Since the quantity L / n A A c
in eq. 16 can be measured or set independently of the test, only the change in
mass with respect to time, Am/At, is measured during the test.
Since, at steady state,
-Aml/At = Am2/At = Am/At (17)
where Aml is the decrease in mass of the chemical species in the source
reservoir; and Am 2 is the increase in mass of the chemical species in the
collection reservoir, either the source reservoir or the collection reservoir
could be sampled during the test (Fig. 2a). However, it is best to sample both
reservoirs to insure that steady-state conditions have been met through eq. 17.
The use of the difference operators in eqs. 16 and 17 implies that the
concentration gradient across the sample is linear. However, due to coupled
flow processes, the concentration gradient within the soil sample may be
nonlinear, as illustrated in Fig. 2b (e.g., see Dutt and Low, 1962; Kemper and
van Schaik, 1966; Quigley et al., 1987). As a result, the D*-values determined
using the external (across the clay) concentration gradient may not be the
L L J
--q-
Cl>C 2 r- -I
C i C2
m
A
i o,,i
Source i Collection
Reservoir | Reservoir
V1
; i!
|
V2
(a)
Experimental •
Theoretical
Level (c)
Qt
dx
(b)
V Volume
=
c Concentration
= i i Ti~
m = Mass (= c x V) TL
Fig. 2. Steady-state method: (a) diffusion-cell (plan or profile); (b) concentration profiles in soil sample; and
(c) time-lag method.
L A B O R A T O R Y D I F F U S I O N TESTING FOR WASTE DISPOSAL A REVIEW 187
same as those determined using the internal (within the clay) distribution of
concentrations (Dutt and Low, 1962; Quigley et al., 1987; Muurinen, 1990).
Advantages and disadvantages of the steady-state method

The advantage of the steady-state method is that D* of reactive solutes can
be measured without having to know the value for R d since, by definition,
there is no retardation of a solute species at steady state; i.e. R d does not
appear in Fick's first law, eq. 7. However, the time required to establish
steady-state conditions with reactive (adsorbing) solutes will be longer than
that for nonreactive solutes, especially for relatively thick samples. The
duration of the test can be shortened by presaturating the exchange complex
of the soil with the reactive solute being used in the test.
A disadvantage of the method is that the mass of the chemical species
diffusing from the source reservoir must be continuously replenished while the
mass of the chemical species diffusing into the collection reservoir is con-
tinuously removed in order to maintain a constant concentration gradient
(Ac) across the sample and, therefore, to establish and maintain steady-state
conditions. Also, the time required to establish steady-state conditions can be
excessive, especially for relatively thick samples. As a result, a great deal of
attention, care, and time is required in the determination of D*-values using
the steady-state method.
Time-lag method
The fact that it requires time to establish steady-state conditions forms the
basis for a method, known as the "time-lag method", commonly used to
obtain the diffusion coefficient, the permeability constant and the solubility of
a gas flowing through a porous membrane (Jost, 1960; Crank, 1975; Comyn,
1985; Rogers, 1985).
In the time-lag method, the soil is initially at zero concentration and the
concentration at the face through which the diffusing substance emerges (i.e.
c2 in Fig. 2a) is maintained effectively at zero concentration. In this case, the
total amount of diffusing substance per cross-sectional area, Q,, which has
passed through the soil approaches a steady-state value as t ---, ~ , or (Jost,
1960; Crank, 1975):
Q, = (nD*c~/L)(t - RdL2/6D *) (18)
where
Q, = i J~dt (19)
o
188 C.D. S H A C K E L F O R D
and cl is the concentration in the source reservoir (Fig. 2a), which is

maintained at a constant value. Eq. 18 is the equation of a straight line on a
plot of Q, vs. time, with an intercept TL on the t-axis given by (Fig. 2c):
TL = RdL2/6D * (20)
Therefore, D* can be calculated using eq. 20 by plotting Q, vs. time and
determining the value for the intercept TL. However, the retardation factor,
R d must be known a priori in order to apply eq. 20 to studies involving reactive
solutes. This method has been used recently by Muurinen (1990) to measure
diffusion coefficients of uranium in compacted sodium bentonite.
Advantage and disadvantage of the time-lag method

Less control of the test conditions is required for the time-lag method vs.
the standard steady-state method since steady-state conditions only have to be
established, not maintained. However, the retardation factor must be known
to use this method for reactive solutes (see eq. 20). Also, the time required to
establish steady-state conditions can be excessive, too. For example, the tests
performed by Muurinen (1990) required 150-200 days.
Transient methods
In general, transient methods utilize solutions either to eq. 10 or eq. 11

when advective flow is allowed to occur or to Fick's second law (eq. 13) in the
absence of advective flow. Several different transient methods have been used
to measure effective diffusion coefficients for chemical contaminants (e.g.,
Olsen et al., 1965; Crooks and Quigley, 1984; Gillham et al., 1984; Rowe et
al., 1985, 1988; Shackelford, 1988a; Shackelford et al., 1989; Shackelford and
Daniel, 1991a, b). These transient methods can be separated into three
categories: (1) column methods; (2) the half-cell method; and (3) reservoir
methods.
Column methods
Constant source concentration

The "traditional" column test has been used extensively in the study of
mass transport through porous media (e.g., see Freeze and Cherry, 1979). The
concept is illustrated in Fig. 3. First, steady-state fluid flow is established
through the soil sample. After steady-state fluid flow has been established, the
fluid in the influent reservoir (usually water) is changed to a solution with
known and constant concentrations (c0's) of particular chemical species. The
concentration, c, of a chemical species appearing in the effluent reservoir is
measured over time, and the results are plotted in the form of solute break-
LABORATORY D I F F U S I O N T E S T I N G FOR WASTE DISPOSAL--A REVIEW 189
Influent With Constant

14[--- Concentration of Chemical
Species, c O
I" (a)
Effluent: Sampled for

Porous / ] i
i I .--b, Concentration,c
Plate
Experimental • Theoretical - -
B
. Nonreactive •
.~ o.5-
"° . _ y i
¢~ 0 I I
1,0
J1 I
2,0
Pore Volumes of Flow ( P V )
Experimental • Theoretical--
Nonreactive i
Solute
~,~ ,... 0.5 .....................................
1.0 21.0
Pore Volumes of Flow ( P V )
Fig. 3. Column test with constant source concentration: (a) test set-up; (b) breakthrough curves when
D* ,~ Dh; and (c) breakthrough curves when D* ~ D h.
through curves, or relative concentration, C/Covs. time or pore volumes of flow

(PV). A pore volume of flow for a saturated soil is the cumulative volume of
flow through the soil sample divided by the volume of the void space in the
soil. Typical breakthrough curves for nonadsorbing and adsorbing solutes are
shown schematically in Fig. 3b. The spreading effect, or "S" shape, exhibited
by the breakthrough curves in Fig. 3 is a result of dispersion of the solute
during transport through the soil. Dispersion causes some of the solute to
appear ahead of the advective front (dashed lines in Fig. 3b) while the
remainder of the solute lags behind the advective front. The ratio of the pore
volumes of flow for the reactive solute to the pore volumes of flow of the
nonreactive solute at a relative concentration of 0.5 typically is taken as the
retardation factor, Rd (Freeze and Cherry, 1979). For example, the value of
Rd for the conditions shown in Fig. 3b is 2.0.
Breakthrough curves such as the ones illustrated in Fig. 3 typically are
modeled using the following analytical solution to eq. 10 (e.g., Bear, 1972,
1979; Freeze and Cherry, 1979):
190 C.D. S H A C K E L F O R D
coC - - ,'W-.', erfc

+ exp~-D-~-h) (.L __+v., (21)
where L is the length of the soil column; erfc is the complementary error
function which, for any argument z, is given by:
erfc(z) = 1 - eft(z) (22)
and eft(z) is the error function of the argument, z, or:
2
eft(z) - x ~ 0f e -~2 d~ (23)
Values of eft(z) and erfc(z) are tabulated in several texts (e.g., Carslaw and
Jaeger, 1959; Crank, 1975; Freeze and Cherry, 1979). Alternatively,
Abramowitz and Stegun (1972) present several mathematical expressions
which can be used to evaluate eft(z).
The initial and boundary conditions upon which eq. 21 is dependent are as
follows (Ogata and Banks, 1961; Ogata, 1970; Freeze and Cherry, 1979):
c(x>lO, t=O) = 0
c(x<~O, t>/O) = Co (24)
c(x=~, t>lO) = 0
The second boundary condition corresponds to that for a semi-infinite
medium which would seem to invalidate the use of eq. 21 for modeling
breakthrough curves from columns of soil with finite lengths. However,
Parlange and Starr (1975) compared eq. 21 and an approximate solution to
eq. 10 based on a boundary condition for a finite column and concluded that
eq. 21 was an adequate model for analyzing breakthrough curves from
laboratory tests using finite columns.
Eq. 21 is utilized by back-calculating values of the hydrodynamic
dispersion coefficient, Dh, for given values of C/Co, L, Vs, t and Rd. A nonreac-
tive tracer such as CI- typically is used so that R d can be assumed as unity.
Once the value of Dh is determined, the effective diffusion coefficient, D*, can
be determined using eqs. 2 and 6 provided the value for the mechanical
dispersion coefficient, Dm, is known. However, since Dm typically is not known
with any degree of certainty, this approach can be difficult in practice.
An alternate approach is to impose very low seepage velocities so that the
effects of mechanical dispersion can be considered negligible, and the effective
diffusion coefficient can be taken as equal to the hydrodynamic dispersion
coefficient, i.e. D* ~ Dh . Under these conditions, the breakthrough curves in
Fig. 3b will be offset to left as shown in Fig. 3c (e.g., see Biggar and Nielsen,
1960; Shackelford, 1988b). For example, Rowe et al. (1988) concluded that
diffusion was the dominant mechanism of transport for tests on intact samples
of an unweathered clay till when the seepage velocity was between 0.064 and
0.09 m yr- ~. However, care must be exercised in this approach as well since the
existence of an "effective porosity, ne", less than the total porosity also can
cause an offset in the solute breakthrough curves. Effective porosities on the
order of 2-30% of the total porosities have been measured in some compacted
clay soils (Horton et al., 1985; Daniel et al., 1989; Liao and Daniel, 1989).
Decreasing source concentration

A modified column test using an initial concentration of a chemical species
in the source reservoir which is allowed to decrease with time has been
described by Rowe et al. (1988). The concept is illustrated in Fig. 4. The
column consists of a source reservoir, a column of soil, and a porous plate use
to collect the effluent from the soil. The test begins when the solution
containing the chemical species of interest at known, initial concentrations, co,
is placed in the source reservoir. As advective and diffusive transport occurs
"; ~-- - - - I Initial Concentration, c

o'
Source I Which Decreases With
Hf Reservoir ~ Time
+x - ~ L
2'__
'~ ~
Soil
la)
_i Effluent: Collected
and Monitored for
Concentration,cb
Porous
Plate
(b) Experimental •
DURING T E S T Theoretical
L
_ --c o
Concentration In
0 Soil Pore Water, c
g~o
L
P 0oji _=~ "(c1i,
In Effluent ~'-= I AFTER TEST
io
I
.
0 Time
Fig. 4. Column test with decreasing source concentration (after Rowe et al., 1988): (a) test set-up; (b) source
and effluent concentrations vs. time; and (c) concentration profile in soil.
t h r o u g h the soil, the concentrations of the specified chemical species decrease

with time in the source reservoir and eventually increase with time in the
effluent collection system. The results are plotted as concentration vs. time
(Fig. 4b), and a semi-analytical solution to the advective-dispersive transport
equation (eq. 10) in the form of the computer program, POLLUTE, is used to
fit theoretical curves to the measured data to determine Dh-values. After the
test is over, the column is disassembled, the soil is sectioned, and the con-
centrations of the chemical species are measured as a function of the depth of
the soil in the column. Once again, POLLUTE is used to fit a theoretical curve
to the measured concentration profile in the soil. The value of D h determined
from the concentration profile is used as a check on the value Of Dh determined
from the variation in source concentration. The theory for the semi-analytical
solution u p o n which POLLUTE is based is presented elsewhere (e.g., Rowe and
Booker, 1984, 1985; Rowe et al., 1985).
Rowe et al. (1988) present the results of laboratory tests in which the
D*-values of several ions in a weathered clay till soil were measured using the
above technique. In their tests, they determined that the advective velocities
were sufficiently low such that mechanical dispersion was negligible, and that
the porosity of the soil calculated on the basis of the water content gave a
reasonable indication of the effective porosity. As a result, Rowe et al. (1988)
concluded that the observed Dh-values were the same as the effective diffusion
coefficients, D*. A m o n g the reported advantages of the technique are (Rowe
et al., 1985, 1988): (1) both D* and R d for retarded solutes can be determined
from the results of a single test; (2) the decreasing source concentration more
correctly models the field situation than does the constant source concen-
tration; and (3) it is easier from a practical standpoint to allow the source
concentration to decrease with time than it is to try to maintain a constant
source concentration.
Advantages and disadvantages of column methods

C o l u m n methods have been used for a relatively long time and, therefore,
one advantage of the column methods is that there is a lot of previous
experience. In addition, it may be advantageous to use the column m e t h o d
when there is an advective c o m p o n e n t of transport (v~) in the field situation.
However, a disadvantage of the column m e t h o d in diffusion testing is that
the effective diffusion coefficient, D*, must be separated from the hydro-
dynamic dispersion coefficient, Dh; therefore, the mechanical dispersion coeffi-
cient, D m, must be k n o w n or the seepage velocity must be sufficiently small in
the test so that mechanical dispersion can be considered to be nil. Such low
seepage velocities typically will require long test durations for all but the
smallest soil samples. When small soil samples are tested, the representative-
ness of the sample to field applications m a y be questioned. C o l u m n tests also
require the determination of the existence and magnitude of an effective

porosity, no.
Half-cell method
The half-cell method is illustrated in Fig. 5. In the half-cell method, two

half-cells of soil are placed together to allow diffusion of solutes to occur via
the liquid phase from one half-cell to the other. If both half-cells are tagged
with tracers, the situation is analogous to the counter diffusion system, i.e.
diffusion occurs in both directions. If only one half-cell is tagged with a tracer,
the system is analogous to the salt diffusion system, illustrated in Fig. 5.
In the salt diffusion case, the initial condition is illustrated by the concentra-
tion profile in Fig. 5b corresponding to time to. As time progresses, the mass
of solute in the tagged half-cell decreases as the solute diffuses into the
untagged half-cell. At infinite time (t 3 in Fig. 5b), the system will be in
equilibrium. At intermediate times, a concentration profile within the cell will
result (e.g., tl and t2 in Fig. 5b). The effective diffusion coefficient can be
determined by disassembling the cell after an elapsed time, t, sectioning the
soil in each half-cell, and determining the concentration profiles of the
specified solutes. Then theoretical profiles can be fitted to the experimental
data by assuming D*-values in an analytical solution to eq. 13. With respect
to this procedure, two cases are of interest: (1) the infinite medium; and (2) the
finite medium.
If the concentration profile does not reach the ends of the cell, the profile
will look like that in Fig. 5c, and the porous medium can be considered to be
infinite in extent. One set of initial and boundary conditions for this case is as
follows:
c ( x ~< O, t=O) = Co; c ( x > O, t = O) =- 0
e(x= --~, t > O) = co (25)

e(x=~, t>O) = 0
and the solution is (Crank, 1975):
c _ l erfc ( v ~ R ~ ) (26)
Co 2 2
When the concentration profile reaches the ends of the cell, the concen-
tration profile will look like Fig. 5d, and the porous medium can no longer be
considered to be infinite in extent. Note that the origin for the x-axis has been
re-defined in Fig. 5d. The appropriate initial and boundary conditions for this
case are:
194 C.D, SHACKELFORD
BEFORE CONNECTING ( ~1) AFTER CONNECTING

Half-Cell Half-Cell
NN
Direction
of Diffusion
...............
t3=oo >t2>tl:Pt0 =0
P +X
0
ir< L ~:
1.0
C/C O
0.5
i1=' X
-X 0 +X
1.0
c/c°
0.5 Experimental •
Theoretical --
0 I) x
0 X° L
Fig. 5. Half-cell method: (a) test set-up; (b) concentration profiles in soil; (c) profile for infinite medium;
and (d) profile for finite medium.
c(x<~O, t=O) = Co; c(x>O, t=O) = 0

Oc(x= O, t > O)/Ox = 0 (27)
t~c(x= L, t > O)/Ox = 0
and the solution is (Barrer, 1951; Carslaw and Jaeger, 1959):

c xo (%
Co L + -Trm=l m cos sin (28)
Eq. 28 has been applied to measure strontium and chloride diffusion coeffi-
cients in compacted bentonite (e.g., Gillham et al., 1984; Robin et al., 1987).
In some cases, it may be more convenient to determine the total mass of
contaminant which has diffused into the untagged half-cell instead of the
resulting concentration profile. This is easily accomplished by utilizing Fick's
first law (eq. 7) to determine the mass flux into the soil at the interface of the
half-cells, and then integrating the flux with respect to the elapsed time to
L A B O R A T O R Y D I F F U S I O N TESTING F O R WASTE DISPOSAL A REVIEW 195
determine the total mass, Mr, which has diffused into the soil after time t, or:
M, t
M, = f dm = A f JDdt (29)
o o
where A is the cross-sectional area of the soil sample.

For the infinite medium case, eq. 26 represents the concentration distri-
bution in the soil, and the diffusive flux into the untagged half-cell is as follows
(Barrer, 1951; Jost, 1960):
Jo = -D*n -~x x=0 = 2 ~/ ~ (30)
When eq. 30 is substituted into eq. 29 and rearranged, an explicit expression

for D* results, or (Barrer, 1951; Jost, 1960):
D* ( Mt ,]2( rc ~ L2 (M'~2(R'J~ (31)
= \~ncoJ \-~dtdt/ = -4-\MoJ \ t /
where co is the initial, liquid-phase concentration of the contaminant in the
tagged half-cell; and M 0 is the initial, total (adsorbed plus liquid phase) mass
of the contaminant in the tagged half-cell (i.e. ~ALnRaco).
For a finite medium, the concentration gradient is determined by taking the
derivative of eq. 28 with respect to x at x = x 0, and the expression for the
total mass of contaminant in the untagged half-cell at an elapsed time t is
(Barrer, 1951):
Mr 4 ~ sin2(mrCxo/L)[ ( m2rdD*t'~]
M0 - Zr2m=l m2 1- exp RoL2 j j (32)
where M0 is as defined in eq. 31. After determining M~, eq. 32 can be used to
solve for D* iteratively.
Advantages and disadvantages of the half-cell method

The half-cell method seems to be the preferred method of soil scientists and,
therefore, there is a lot of data available in the literature on the measurement
of effective diffusion coefficients using the half-cell method. In addition, the
data from the half-cell method are relatively easy to analyze particularly since
the concentration profile is not required.
However, it may be difficult in practice to develop full contact between the
two half-cells, especially for relatively large soil specimens. Also, it may be
difficult and/or time consuming to saturate unsaturated soil samples, and the
boundary condition may not be appropriate for the application of the test
results (e.g., use of the soil as a clay liner for the containment of liquid wastes).
Reservoir methods
Double reservoir method

A double reservoir method has been described by Rowe et al. (1988). The
set-up is essentially the same as in Fig. 4 except there is no advective flow
(vs -- 0) and the porous plate used for effluent collection in Fig. 4 is replaced
by a second reservoir as shown in Fig. 6. Also, the contaminant accumulates
in the collection reservoir and is sampled, not removed.
The concentration profiles in the source reservoir, soil and collection
reservoir as a function of time resulting from the double reservoir method are
illustrated in Fig. 6b. The experimental data that result from the test are
essentially the same as those for the column method with decreasing source
concentration, shown in Fig. 4, and can be analyzed for D*-values using
POLLUTE as previously described.
The progression of the concentration profiles in Fig. 6b is of interest in that
at time t3, steady-state conditions have been reached. Therefore, the double
reservoir method represents the transient conditions which precede the
establishment of steady-state condition in the steady-state test.
Initial Concentration, Co,

Source Which Decreases Wilh
Hf ~~Reservoir Time
+x"-~-- L
Hr Effluent: Sampled
~ t e°IsleerC:
'oin for Concentration, cb
(a)
0 c3 c 2 C1 CO
tI to= 0
•xTiI
-" Ct
Soil
Ib Cb
to < t1 < t2 < t3

t 2
(b)
Fig. 6. Double reservoir method: (a) test set-up and (b) concentration profiles.
L A B O R A T O R Y D I F F U S I O N TESTING F O R WASTE D I S P O S A L - A REVIEW 197
Advantages and disadvantages of the double reservoir method

The advantage of the double reservoir method over the column method is
that Dh = D* since vs = 0. The advantage over the steady-state method is
that steady-state conditions do not have to be established and, therefore, the
test is easier to perform and the test duration can be reduced. However, since
vs = 0, the test duration will be longer than the column method for a similar
size of sample. In addition, it may be difficult and/or time consuming to
saturate the soil sample prior to the start of the diffusion test.
Single reservoir methods

The set-up for the single reservoir methods is the same as the double
reservoir method except the collection reservoir is removed. The single
reservoir methods, like the column methods, can be separated into two types
based on whether the source concentration is allowed to decrease with time
or is maintained at a constant concentration.
Constant source concentration The concentration profiles resulting from a

constant concentration of the contaminant in the source reservoir are illus-
trated in Fig. 7. The D*-values can be determined by sectioning the soil after
an elapsed time, t, determining the resulting concentration profile with depth
in the soil, and fitting theoretical curves to the measured data by assuming
different D*-values in a solution to eq. 13. Two cases are of interest, viz. the
semi-infinite medium case and the finite medium case.
The initial and boundary conditions for the semi-infinite case, illustrated in
Fig. 7c, are the same as presented for the column method with a constant
source concentration, and the solution is (Carslaw and Jaeger, 1959; Crank,
1975):
c _ erfc(~) (33)
co 2
which can be derived from eq. 21 by letting vs equal zero. This equation has
been used recently by Idemitsu et al. (1990) to measure the apparent diffusion
coefficients, D] ( = D*/Rd), of plutonium in compacted bentonite.
For the finite porous medium case (Fig. 7d), the boundary condition at the
bottom of the soil sample (x = L in Fig. 7a) becomes:
Oc/~x = 0 (34)
which essentially states that no flux of contaminant exits the bottom of the soil
sample. In this case, a solution for the resulting concentration distribution in
the soil at any time t is (Crank, 1975):
C 4 5"~ (--1)m exp --
Co
1
-- ~ ~";'--0=2m + 1 I +
4-R~Lf J cos +
2-L 1(35)
Initial Concentration, c ,
Source --Which Remains Constan~
Hf Reservoir
r
0 to= 0 Co
÷x~L Soil = 0 I ~:
],l A
/,2 {,3 Soil
" Bottom of Soil Sample
r to < tl < t2 < t3

(a) +x
(b)
Relative Concentration, c/c O

0 1.0
= 0 I •
Experimental •
Theoretical
_=
I, oil Sample
r
+x (c)
Relative Concentration, ctc

Source
0 1.0 ° Hf Reservoil
- 0 I •
_=
a
f
Bottom of Soil Sample
"'L'J_ Soil
I
.x (d) (e)
Fig. 7. Single reservoir method with constant source concentration: (a) test set-up; (b) concentration
profiles in soil; (c) profile for semi-infinite medium; (d) profile for finite medium; and (e) positive x-direction
for finite medium case.
where the positive x-direction of the cell is defined in Fig. 7e. Eq. 35 can be
used to back-calculate D*-values given the concentration distribution in the
soil. As an alternative, the total mass of contaminant in the soil at the end of
the test, M,, can be measured and used in the following equation to determine
D* (Crank, 1975):
_ _ 8 [ +
Moo m=O (2m + 1)=rd exp - 4RdL 2 j (36)
where Moo is the corresponding total mass of the contaminant in the soil at
infinite time (i.e. at equilibrium), which is given by:
Moo = ALn Raco (37)
This case also can be analyzed for other initial and boundary conditions using
the POLLUTEmodel previously described.
As with the steady-state method, the practical difficulty of maintaining a

constant concentration in the source reservoir may result in a labor-intensive
and time-consuming experiment. Also, frequent replacement of the contami-
nant solution may result in undesirable fluctuations in the diffusive transport
into the soil (Rowe et al., 1985). As a result, a decision must be made as to
the correct interval to use for replacement of the source solution.
Decreasing source concentration The test set-up for the single reservoir case
with a source concentration which decreases with time is illustrated in Fig. 8a.
The resulting concentration profiles in the soil as a function of time are shown
in Fig. 8b. Like the column method with decreasing source concentration and
the double reservoir method, the D*-values can be determined not only from
the concentration profile of the contaminant in the soil at the end of test (Fig.
8c and d), but also from the decrease in source concentration with time during
the test (Fig. 8e). Again, semi-infinite and finite boundary conditions should
be considered as separate cases.
-F
Initial Concentration, c ,
Source _ _ Which Decreases With o
Hf Reservoir Time
Experimental •
(a) Theoretical --
_,_ ~
0 C3 C2 Cl Co
--~;- ~;...~. I I a ct
, ~ to= 0
L (t3 Soil to < t 1 < t2 < t3

t2 (b)
+x~' Bottom of Soil Sample
-/
0 Concentration In Soil, c 0 Concentration Irl Soil, c
0 b 0 • b
oil ~ Soil
c c
3ottom of Soil Sample . Bottom of Soil Sample
g
+xl (c) +x I,
(d)
.~ co Source Reservoir
~ c
~• o
0 I Time
o (e)
Fig. 8. Single reservoir method with decreasing source concentration: (a) test set-up; (b) concentration
profiles in soil; (c) profile for semi-infinite medium; (d) profile for finite medium; and (e) concentration in
source reservoir vs. time.
For the semi-infinite case, the concentration profile has not reached the end
of the soil sample (time t~ in Fig. 8b, and Fig. 8c). One set of initial and
boundary conditions for this case is as follows (Carslaw and Jaeger, 1959;
Crank, 1975):
c(x ~ O, t=0) = Co; c(x > O, t = O) = 0
Oc(x = O, t > O)/Ox = -(D*Rdn/HO.~c(x = 0, t > O)/Ox (38)
c(x=~, t>O) = 0
where the positive x-direction has been defined with respect to Fig. 8a. An
analytical solution for these initial and boundary conditions is (Carslaw and
Jaeger, 1959):
Co expL--- - -t- D*Rdl erfc x + ~ (39)
Eq. 39 can be used to back-calculate D*-values given the concentration profile

in the soil, i.e. c = f(x); the effective height of the source reservoir (H0; the
initial concentration of the contaminant (co); the porosity of the soil (n); the
retardation factor of the contaminant (Rd); and the duration of the test (t)
(e.g., Desaulniers, 1986).
The change in the contaminant concentration in the source reservoir with
time (Fig. 8e) can also be used to determine D*-values for the semi-infinite
case simply by setting x = 0 in eq. 39 (e.g., Myrand et al., 1989), or:
c, exp [ ( ~ ) 2 D,Rd ,1 erfc ( ~ ~ ) (40)

Co
where c, is the contaminant concentration in the source reservoir as a function

of time. Eq. 40 has been presented in a slightly different form by Crank (1975),
or:
Mt - (1 + ~) 1 - exp erfc g ~ (41)

Moo
where M, is the total mass of solute in the soil at time t, and c~is a coefficient
for the given solute, or (Shackelford, 1988a; Shackelford et al., 1989):
c¢ = Hr/nRdL (42)
From consideration of mass balance, the equilibrium mass, M~, in the soil is
related to the initial mass of the contaminant in the source reservoir, M0, as
follows:
Moo = [1/(1 + ~¢)]M0 = [1/(1 + c¢)]AHfc o (43)
where A is the cross-sectional area of the source reservoir. The ratio M ~ / M o

[= 1/(1 + ,)] in eq. 43 is known as the "final fractional uptake, F F U " of the
solute by the soil (Crank, 1976; Shackelford, 1988a). For larger arguments of
the complementary error function in eq. 40 or eq. 41, the following alternate
solution may be required for the analysis (Crank, 1975; Shackelford, 1988a):
co ~ 1 2z2 + 4z4 8z 6 + . . . (44)

where
n x/-~oD*t (45)
z -- Hf
Eq. 44 results from substituting the asymptotic expansion given by

Abromowitz and Stegun (1972) for exp (z2) erfc(z) in eq. 40. Eq. 44 is appro-
priate for analysis when z2 is large, which occurs with very high fractional
uptakes of the solute by the soil, e.g., large Rd-values (Crank, 1975).
When z ~> 1.0, eq. 44 reduces to:

ct Hf
- (46)
CO ? / ~
in which case D* can be solved for directly for a given concentration ratio,
Ct/Co"
For the finite porous medium case (tz in Fig. 8b, and Fig. 8d), the second
boundary condition in eq. 38 becomes that of eq. 34, and eqs. 39-41 and 44
should not be used to evaluate D*-values. Instead, the D*-values may be
determined using POLLUTEwith both the concentration profile within the soil
at the end of test and the variation in source reservoir concentrations with
time. As an alternative to the latter technique, the following analytical
solution may be used (Crank, 1975; Shackelford, 1988a; Shackelford et al.,
1989):
M, = 1 -- ~ 2~(1 + ~) ( D*q~t']
M~ m=, 1 + ~ + ~2q~ exp ~-~o~--~
] (47)
where the qm'S in eq. 47 are the non-zero positive roots given by:
tanqm = -- ~qm (48)
Values of qm as a function of ~ and the F F U are given in Crank (1975) and
Shackelford (1988a). Usually, the analytical solution converges very rapidly;
therefore, only one or two terms are required in the series summation in eq.
47.
Advantages and disadvantages of the single reservoir method

Like the double reservoir method, Dh = D* for the single reservoir
methods since Vs = 0. In addition, transport through the soil sample is not
required, so the test duration can be reduced over that required for the double
reservoir method. Also, the boundary condition between the source reservoir
and the soil sample is analogous to the boundary condition in the field
between the leachate being contained in the clay barrier (e.g., see Fig. la).
However, like the double reservoir and steady-state methods, it may be
difficult and/or time consuming to saturate an unsaturated soil sample prior
to the start of the diffusion test.
Additional considerations
Saturated vs. unsaturated soils

Soils used for waste containment barriers are often unsaturated. This is
particularly true if the barrier is considered to be that portion of a natural soil
deposit (e.g., aquiclude, aquitard) or a man-made barrier (e.g., compacted
clay liner) between the waste material and the water table. Therefore, mea-
surement of specific D*-values for unsaturated soil represents the most
realistic approach for actual situations involving containment barriers.
The equations presented thus far for the various methods for measuring D*
are equally applicable to tests on unsaturated soils if the volumetric moisture
content, 0, is used in place of the porosity, n. The volumetric moisture content
is defined by the following relationship:
0 = nSr (49)
where 0 represents the volume of moisture or solution per total volume of soil;
and the degree of saturation, Sr, is expressed in decimal form. However,
diffusion testing of unsaturated soil also requires that the soil suction be
controlled in order to prevent mass flow of the contaminants due to suction
gradients. While laboratory diffusion testing of unsaturated soil has been
performed in a number of instances (e.g., see tension plate approach used by
Klute and Letey, 1958, or the approaches used by Graham-Bryce, 1963, or
Conca and Wright, 1990), the experiments generally are more difficult to
perform.
In addition to the greater difficulty of performing diffusion tests on un-
saturated soils, there are three practical reasons for performing laboratory
diffusion tests on saturated soils:
(1) the maximum liquid-phase diffusive flux will occur when the soil barrier
is saturated due to the increased cross-sectional area of flow at saturation, all
other factors being equal (see eq. 7);
(2) the effective diffusion coeffÉcients of contaminants in unsaturated soils
typically are less than those in saturated soils due to the increased tortuosity
(lower z-values) of the flow paths in unsaturated soils; and
(3) the suitability of many landfill sites currently is being based on analyses
which assume saturated parameters (e.g., saturated hydraulic conductivity).
As a result of the greater degree of conservation and practicality of testing
soils that are saturated, diffusion testing in practice likely will be performed
routinely only on saturated soils samples.
Saturation methods
Two methods commonly are used to saturate an unsaturated soil in the

laboratory: a permeation method and a soaking method. In the permeation
method, a relatively high hydraulic gradient is used to force several pore
volumes of saturating solution through the soil thereby increasing the degree
of saturation of the soil. The advantage of this method is that the hydraulic
conductivity of the soil with respect to the saturating solution can be
determined once steady-state flow has been established. The disadvantage is
that the use of a relatively high hydraulic gradient can cause disturbance to
the soil sample due, in part, to particle migration and excessive seepage forces
(e.g., Mitchell and Younger, 1967; Olson and Daniel, 1979).
In the soaking method, the soaking solution is allowed to flow, or infiltrate,
into the soil under a gradient established partly by gravity and partly by the
negative pore water pressures, or suction, in the unsaturated soil. The soil
sample can be soaked from one or both ends using a variety of techniques. For
example, the soil sample can be immersed totally in soaking solution or, in the
reservoir methods, the soaking solution can be introduced into the reservoirs
for a short period and removed before the diffusion stage of the test
commences. However, these techniques may be time consuming and ineffi-
cient since the air is being displaced in a direction opposite to the direction of
the infiltrating solution. An alternative technique is to expose only the base of
the soil sample to the soaking solution thereby allowing the soaking solution
to infiltrate into the soil by capillarity. In this way, air is more readily
displaced through the top of the sample. In addition, a vacuum can be applied
to the top of the sample to speed the process.
Another method commonly used by geotechnical engineers to saturate soils
in shear strength testing of soils is "back-pressure saturation" wherein the
sample is exposed to soaking solution under an applied (positive) back
pressure (e.g., see Bishop and Henkel, 1962). The applied pressure forces air
into solution in accordance with Henry's law and, thus, relatively high degrees
of saturation (St /> 95%) usually can be achieved in relatively short periods
(~<1 week) using high applied pressures (e.g., ~>410kPa or 60psi). In
addition, the soil sometimes is pre-saturated with a gas other than air [e.g.,
carbon dioxide, C 0 2 , which has a higher equilibrium (Henry's law) constant],

to increase the efficiency of the procedure. However, if the concentration of
air or other gas in solution is excessive due to back pressure, the condition for
chemical reactions (e.g., redox, acid-base, carbonate, etc.) occurring within
the soil may not be representative of those expected in application of the test
results. Therefore, this method is not recommended for diffusion testing.
Finally, in presenting the analytical solutions for determining D*-values,
the thickness, L, of the soil is assumed to be fixed and remain constant as the
diffusion test proceeds. As a result, soils which swell during soaking will have
to be trimmed flush with the cell before the diffusion stage of the test begins
so as not to invalidate the analysis for D*. As an alternative, Crank (1975)
discusses the modifications required to eq. 36 if the soil is not pre-soaked and
swelling is allowed to occur during diffusion.
Sectioning and extracting procedures
Many of the methods for measuring D* require that either the concentra-
tion profile of the contaminant or the total amount (mass) of contaminant
within the soil be known at the end of the test. As a result, it may be necessary
to section the soil into slices at the end of the diffusion test and to extract the
contaminant species from the soil for chemical analysis. The sectioning
procedure typically involves controlled extrusion of the soil sample from the
diffusion cell and slicing the soil into thin sections at selected intervals. For
example, Brown et al. (1964) and D. Barraclough and Nye (1979) describe a
quick-freeze technique in which half-cells of soil were frozen, and the frozen
soil was then extruded from the cells and partitioned into sections up to a
thickness of 50 ~tm using a refrigerated microtome. Shackelford (1988a) used
a modified load frame to extrude and section kaolinite and a natural smectitic
clay soil into slices ,-~2.54mm (0.1 in) in thickness. The soil samples were
sliced with either a fishing line or a stainless steel knife or beveled plate. The
fishing line worked well for the soft kaolinite samples, but not as well for
relatively stiff nonuniform consistency of the natural clay soil. Other
sectioning techniques are described by Tinker (1969) and Gillham et al.
(1984).
After the soil has been sectioned, the concentrations of contaminants in
each slice must be determined. Three methods commonly are used to extract
the contaminants from the soil: (1) high-pressure pore water squeeze
(HPPWS); (2) chemical extraction; and (3) chemical digestion. The HPPWS
technique is similar to a consolidation test in which the pore fluid within the
soil slice is forced out under high pressure and analyzed for contaminant
concentrations. For example, Crooks and Quigley (1984) used a high-pressure
consolidation device to obtain pore water samples by squeezing soil samples
under a vertical pressure of 23.5 MPa (3400 psi) for 12 h. Johnson et al. (1989)
used a nitrogen source to apply pressures up to 4.1 MPa (600 psi) to remove
pore water samples from recovered soil cores. Similar techniques are described
elsewhere (e.g., Goodall and Quigley, 1977; Rowe et al., 1988).
The concentration of contaminants in the pore water from the HPPWS
technique are the free (liquid phase) concentrations, c (i.e. the adsorbed
concentrations are not determined). The other two extraction techniques
- - c h e m i c a l extraction and d i g e s t i o n - result in the measurement of the total
(free plus adsorbed) concentrations of the mobile contaminants in the soil
slice. Since the free concentration profile is required for the analysis of D* the
total concentrations of the mobile species determined in the chemical
extraction and digestion techniques must be divided by the retardation factor,
Ro, to provide the free concentration profile, or:
C = CT,m/R d (50)
where c~-m is the total (adsorbed plus free), measured concentration of the
mobile species based on volume of solution in soil. For nonreacting (nonad-
sorbing) chemical species, R d is unity and CT,m equals c.
In the chemical extraction technique, the soil from each soil slice is mixed
with an extracting solution specially prepared to remove the contaminant
species of interest from the soil. De-ionized distilled water (DDW) has been
used to extract nonreactive (anion) chemical species (e.g., Gillham et al., 1984;
Shackelford, 1988a; Shackelford et al., 1989). The extracting solution for
exchangeable ions typically is an acid solution (e.g., HNO3) or a solution
containing either a competing ion or a complexing ligand species, i.e,, a
chelating agent (e.g., ethylenediaminetetraacetate or EDTA). For example,
Farrah and Pickering (1978) examined the ability of 17 different chemical
solutions to displace heavy-metal ions (Pb, Zn, Cu and Cd) pre-adsorbed to
the exchange sites of clay (kaolinite, illite and montmorillonite) at either pH 5
or 7. They found that only EDTA (0.001 M, pH 7) quantitatively released all
four ions from each of the three clays. Procedures and extracting solutions for
other chemical species and soils are described elsewhere (e.g., Tucker and
Kurtz, 1955; Chester and Hughes, 1967; Tinker, 1969; S.K. Gupta and Chen,
1975; Silviera and Sommers, 1977; Guy et al., 1978; Lindsay and Norvell,
1978; Tessier et al., 1979; Lake et al., 1984).
In the digestion techniques, the non-mobile metals associated with the
primary and secondary minerals (residual fraction) of the soil, as well as the
mobile metal species (adsorbed plus liquid phase), are determined. The con-
centrations of the nonmobile metal species are determined on separate
samples of soil and then subtracted from total (nonmobile plus mobile) metal
concentrations resulting from the digestion procedure to provide an estimate
of the mobile (adsorbed plus liquid phase) metal concentrations. This
procedure usually is done by alkaline fusion or dissolution of the soil with

mixtures of hydrofluoric acid and some other strong acid, e.g., nitric or
perchloric acid (Tessier et al., 1979). Other procedures for digestion are
provided in Page et al. (1982) and Greenberg et al. (1985). The results of the
study by Tessier et al. (1979), as well as others, illustrate the difficulty of
distinguishing between background concentrations and mobile concentra-
tions when only total metal analyses are performed. Therefore, it may be
difficult, in practice, to utilize digestion techniques to determine contaminant
concentration profiles in soils when there is a significantly high background
(nonmobile) concentration of the contaminant species in the soil.
As an alternative to sectioning and extraction, Evans and Barber (1964)
took autoradiographs using X-ray film to follow the movement of the radio-
isotope, 86Rb+, in their diffusion cell apparatus. The advantage of this
technique is that the concentration profile can be determined during the
diffusion test as well as at the end of the test.
Organic chemicals
Extra precaution should be exercised in the diffusion testing of organic

compounds. For example, Myrand et al. (1989) measured the effective
diffusion coefficients of four volatile compounds of environmental concern
(benzene, trichloroethylene, toluene and chlorobenzene) using core samples of
unsaturated, unweathered glaciolacustrine clay. To avoid losses of the
compounds, the entire diffusion cell apparatus was constructed of stainless
steel, and Teflon ® washers were used between the end caps and column. The
procedure was the same as that for the single reservoir method with decreasing
source concentration except the concentration profiles in the clay were not
measured for two reasons (Myrand et al., 1989): (1) the time required to
develop a measurable concentration profile would have been excessively long
due to the reactive nature of the organic compounds; and (2) the long times
required for measurement of a concentration profile would increase the
opportunity for losses of the volatile organic compounds. In addition, it is not
clear how a concentration profile of a volatile substance could be measured
without incurring significant experimental error. As a result, Myrand et al.
(1989) used eq. 40 (not eq. 39) to measure the effective diffusion coefficients.
Variable D* and nonlinear adsorption behavior
The analytical solutions presented thus far are based on two important
assumptions, viz. the effective diffusion coefficient, D*, is assumed to be a
constant and the sorption (ion exchange) process is assumed to be linear.
However, with respect to diffusion testing for waste disposal, these

assumptions may not always be valid.
For example, Shackelford (1988a), Shackelford et al. (1989), and Shackel-
ford and Daniel (1991b), measured adsorption isotherms of metal species at
concentrations which were more typical of those in actual landfill leachates
and found that the adsorption behavior was nonlinear. They found that the
existence of the nonlinear adsorption behavior made evaluation of the
diffusion test data difficult using analytical solutions.
In general, the existence of a variable D* and/or nonlinear adsorption
behavior makes the resulting differential equation nonlinear which usually
must be solved by numerical techniques. Such numerical techniques generally
are more involved and, therefore, are beyond the scope of this paper. Crank
(1975) provides a review of various methods of solution, including numerical
methods, for the cases when D* is not constant. Crank (1975) also notes that
when methods which assume constant diffusion coefficients are applied to
systems in which such an assumption is not valid, a mean value of D* is
obtained. In addition, the use of a single, constant value for R d when the
adsorption behavior is nonlinear could affect greatly the determination of the
free (liquid phase) concentrations, c, in the soil in accordance with eq. 50 (e.g.,
Shackelford et al., 1989; Shackelford and Daniel, 1991b).
Quality assurance~quality control measures
Several quality assurance/quality control (QA/QC) measures should be

performed in diffusion testing. These QA/QC measures should include mass-
balance analyses, and pH, electrical conductivity (EC) and temperature
measurements. Blank (control) tests, i.e. tests without soil, should be
performed to account for losses of chemical species due to the test apparatus.
In addition, mass balances of the chemical species used in the diffusion tests
should be performed at the end of the test to determine if there is experimental
error and/or if chemical reactions (e.g., precipitation) may have occurred
during diffusion testing. Such losses could affect significantly the interpre-
tation of test data and the resulting determination of D*-values.
In order to evaluate the mass of a given chemical species in the soil, the
concentrations of the contaminants in the soil must be measured. If the
HPPWS technique is used to determine the concentrations of the metal species
in the soil, the resulting concentrations must be multiplied by the retardation
factor in accordance with eq. 50 in order to account for the total mass
(adsorbed plus liquid phase) of the metal species in the soil. This is not the case
for the chemical extraction and digestion techniques. However, inefficient
extraction of the metal species can lead to significant errors in mass balance
(e.g., Shackelford, 1988a; Shackelford et al., 1989; Shackelford and Daniel,

1991b).
The pH and temperature of the contaminant solution and soil should be
measured since chemical reactions, including ion exchange, are known to be
functions of pH and temperature (e.g., Stumm and Morgan, 1981). The EC
measurement can provide an indication not only of the ionic strength of the
solution but also the transport processes occurring during the soaking and
diffusion stages of the test (e.g., Shackelford, 1988a; Shackelford et al., 1989).
SUMMARY OF EFFECTIVE DIFFUSION COEFFICIENTS

Values for D* or D* taken from the results of several studies are presented
in Table 2. The data presented in Table 2 should be viewed with caution since
an interpretation by the author was required in some cases. For example, the
soils used in the diffusion tests performed by Clarke and Graham (1968)
actually were unsaturated, but the authors indicated that the moisture
tensions were so low that the soils could be considered essentially saturated.
In general, effective diffusion coefficients for anions are higher than those
for cations. However, the values for tritium (3H+), which range from
4.5.10-1° to 1.7" 10 -9 m 2s -l, are within the range of the other values reported
for the nonreactive anions. This is to be expected since tritium is considered
a nonreactive solute. The effective diffusion coefficients for all other cations
generally are lower and cover a much broader range of ~ 1.0"I0 -t6 to
2.5" 10 -9 m 2 s -I . The lower values for cations can be attributed to the effect
of adsorption on the cations during transport and to the fact that some of the
values reported for cations are actually D*-values, not D*-values.
The values for the effective diffusion coefficients given in Table 2 are
summarized in Table 3. Several points of interest should be noted. For
instance, the range of D*-values reported for both nonreactive and reactive
solutes in saturated soils is essentially the same. However, the D*-values for
the reactive solutes in saturated soils can be as much as 5000 times lower than
the corresponding D*-values. Therefore, the diffusive transport rates of
reactive solutes can be much lower than those for the nonreactive solutes even
though the D*-values for both nonreactive and reactive solutes are the same
(i.e. D*-values include the effect of R a whereas D*-values do not).
For unsaturated soils, the range of D*-values for reactive solutes is about
an order-of-magnitude lower than the corresponding range for the nonreac-
tive solutes. However, this relatively small difference may be due to the
incorporation of 0 into the definition of D* and/or to the different degrees of
saturation (or unsaturation) in the different diffusion tests. Nonetheless, the
D*-values in unsaturated soil are 2-40,000 times lower than the corresponding
D*-values for the reactive solutes and 20-630,000 times lower than the D*-
~4
TABLE 2 >
Effective d i f f u s i o n coefficients f o r selected c h e m i c a l species 0

7o
>
Chemical Soil(s) System of Diffusion coefficient Reference(s) 0
species* i measurement,2
type form value(s)
(10 l0 m 2 s J)
(A ) Saturated soils."
Z
36CI- sand HC self Dot 5.6 Clarke and G r a h a m (1968)
loam 7.1
clay 6.1
sand-bentonite HC salt DO~ 7.0-10 Gillham et al. (1984)
CI- silty clay loam; sandy loam HC counter Do'C 1.6-4.4 P.B. Barraclough and Tinker (1981) ©
silty clay CCC salt D0"r 6,10 Crooks and Quigley (1984)
clay till CDC salt DOz 5.7-6.3 Rowe et al. (1988)
kaolinite SRDC salt D0"r 4.4 10 Shackelford (1988a)
clay soil 1.5-4.7 m
Br- silty clay loam; sandy loam HC counter O0r 3.7-6.4 P.B. Barrclough and Tinker (1981)
soil cores (field) HC counter Doz 5.0-7.0 P.B~ Barraclough and Tinker (1982) a
kaolinite SRDC salt D0r 4.8-9.9 Shackelford (1988a)
clay soil 1.0-18
i
3H + sand-bentonite HC salt D 0r 8.0-17 Gillham et al. (1984)
kaolinite HC self D0r 5.3 10.9 Phillips and Brown (1968)
<_
montmorillonite 4.5-9.0 r~
32p montmorillonite HC self D0r 0.017-0.12 Phillips et al. (1968)
kaolinite 0.0028-0.22
illite 0.0002-0.0034
silt loam 0.0050-0.0350
clay loam 0.0086-0.0400
K+ clay till CDC salt D0r 6.3, 3.0 Rowe et al. (1988)
kaolinite SRDC salt Dot 12 18 Shackelford (1988a)
clay soil
Na + silty clay CCC salt D(~r 2.5, 3,5 Crooks and Quigley (1984)
clay till CDC salt Doz 4.8, 5.7 Rowe et al. (1988)
T A B L E 2 (continued)
Effective d i f f u s i o n coefficients f o r selected c h e m i c a l species
Chemical Soil(s) System of Diffusion coefficient Reference(s)

species* 1 measurement,2
type form value(s)
(10 - 1 0 m 2 s - I )
(A) Saturated soils (Cont.):

S6Rb+ kaolinite HC self Dot 2.4 Phillips and Brown (1964)
silt loam 1.2
clay loam 0.68
montmorillonite 0.54
kaolinite counter Doz/R d 0.82
silt loam 0.61
clay loam 0.48
montmorillonite 0.39
Ca 2+ clay till CDC salt Doz 3.8 Rowe et al. (1988)
Cd 2+ kaolinite SRDC salt Dot 3.2-7.6 Shackelford (I 988a)
clay soil 3.0-10
Cu 2+ kaolinite SRCC salt Do r / R d 4.2 Ellis et al. (1970a)
montmorillonite 0.27-0.95
Fe 2+ montmorillonite SRCC salt Do~:/ R d 1.0 Ellis et al. (1970b)
Fe 3+ montmorillonite SRCC salt Doz/R d 0.16-0.44 Ellis et al. (1970b)
Mn 2+ kaolinite SRCC salt Doz/R d 4.5 Ellis et al. (1970a)
pu 4+ bentonite SRCC salt Doz/R d < 0.0001-0.03 Idemitsu et al. (1990)
85Sr2+ sand-bentonite HC salt Doz/R d 5.0-20 Gillham et al. (1984)
895r2+ clay soil SRDC self Do~/Ro 0. I-0.12 Mort and Nye (1968)
Zn 2+ kaolinite SRCC salt Doz/ R d 5.1 Ellis et al. (1970a)
kaolinite SRDC salt Doz 3.5-10 Shackelford (1988a)
clay soil 1.5-25
C6H 6 clay till SRDC salt Doz/R d O. I 1 Myrand et al. (1989)

TCE 0.06
Toluene 0.04
C6HsCI 0.03
( B) Unsaturated soils:
36C1- silt loam HC counter D0r 0.63-12 Warncke and Barber (1972a)
1.0-11 Warncke and Barber (1972b)
CI- sandy loam HC self DorO 4.1 7.0 D. Barraclough and Nye (1979)
NO~- glass beads HC counter Doz 15 Romkens and Bruce (1964)
sand 14
silt 13
32p silty clay loam SS, HC self DozO 0.04-1.55 D. Barraclough and Nye (1979)
86Rb+ clay; sandy loam; silt HC self DozO 0.056-0.155 Graham-Bryce (1963c)
loam HC self Doz/Rd 0.064-0.450 Patil et al. (1963)
1°9Cd2+ silt loam; loam HC counter Doz[Rd 0.000052-0.00032 Mullins and Sommers (1986)
6-SZn natural soil HC self Do~/R,I 0.006-0.82 G.N. G u p t a and Deb (1982)
silt loam; loam HC counter Dor/Ro 0.000018-0.0017 Mullins and Sommers (1986)
silt loam HC counter Doz/Rd 0.000001 Warncke and Barber (1972a, b)
silt loam HC counter Dor/Rd O.I Warncke and Barber (1972a, b)
,-t
, I T C E = trichloroethylene.
"2SS = steady state; CCC ~ column with constant source concentration; CDC = column with decreasing source concentration; HC ~ half-cell; SRCC = single reservoir with
v
constant source concentration; SRDC = single reservoir with decreasing source concentration.
>
t'-'
I
7o
D'I
.<
TABLE 3
Summary of effective diffusion coefficients
Type of Form of dif- Range of effective diffusion coefficients

solute fusion coefficient (10-1°m2 s l)
saturated soil unsaturated soil
Nonreactive D* 1.0-18 0.63-15

Reactive D* 0.54-25 0.04-1.55
D~ 0.0001-20 0.000001-0.82
values for the nonreactive solutes. Undoubtedly, the Rd-values for the reactive
solutes diffusing in unsaturated soils are much higher than in saturated soils
due to the close proximity of the diffusing chemical species to the surface of
the soil particle. As a result, the diffusive transport of reactive solutes in
unsaturated soils can be significantly reduced relative to that of the nonreac-
tive solutes in unsaturated soils.
Overall, the D*-values for both nonreactive and reactive solutes in
saturated soils are as much as 10-20 times greater than the corresponding
values in unsaturated soils. The lower values for D* for tests performed on
unsaturated soils reflect the effects of reduced cross-sectional area for
transport, increased tortuosity and increased viscosity of the water (solvent)
near the surface of the soil particle. In addition, the diffusive transport rates
of reactive solutes in unsaturated soils can be as much as 20-100 times slower
than the corresponding rates in saturated soils. These differences in D*- and
D~,-values between unsaturated and saturated soils generally are much greater
than the differences due to other physical factors; e.g., dry density of the soil,
soil pore size and clay content (see Shackelford, 1988a).
The results of this summary suggest that the major factors affecting
laboratory measured diffusion coefficients for soils are the degree of
saturation of the soil and whether or not the diffusing chemical species is
reactive, i.e. is subject to ion-exchange reactions.
SUMMARY AND CONCLUSIONS
In the absence of coupled flow processes, the case of pure diffusive mass
transport of a chemical species represents the limiting transport process
through an earthen barrier. As a result, the best barrier that can be built is one
in which diffusion is the sole transport process (i.e. if coupled flow processes
are negligible). The existing evidence suggests that diffusion will be dominant
when the seepage velocity is on the order of ~<0.005 m y r - I. Such low seepage
velocities generally are associated with transport through fine-grained (e.g.,
clayey) soils. Since fine-grained soils typically are used as waste containment
barriers, it is apparent that laboratory diffusion testing will become a
necessary component of the overall design and evaluation processes
associated with waste disposal practice.
The laboratory methods for determining liquid-phase diffusion coefficients
of chemical species diffusing through fine-grained soils were presented. Both
steady-state and transient methods were considered. The transient methods
include the column method, the half-cell method, the double reservoir method
and the single reservoir method. The appropriate analytical solutions required
to calculate the diffusion coefficients from the laboratory data also were
presented.
The major difference between the column method and the other transient
methods is that advective flow is allowed to occur in the column method. In
addition, the conditions of the test may vary depending on whether or not the
source concentration of the contaminant is allowed to decrease with time, and
whether or not the contaminant is allowed to reach the effluent end of the soil.
Care must be taken to insure that the appropriate analytical solution is being
used for the experimental conditions of the diffusion test.
Two methods for saturating unsaturated soils prior to the start of diffusion
testing are described. The permeation method can provide information on the
hydraulic conductivity of the soil and typically requires less time than the
soaking method. However, the soaking method may model the field situation
better and may result in less disturbance to the soil (e.g., due to excessive
seepage forces).
Three methods - - high-pressure pore water squeeze (HPPWS), chemical
extraction and chemical digestion - - for extracting contaminant species from
the soil at the end of diffusion testing were described. Extraction of contami-
nants is required whenever the concentration profiles or total mass of the
contaminant which has diffused into the soil is desired for effective diffusion
coefficient (D*) or mass-balance determinations. The HPPWS technique
directly determines the free (liquid phase) concentrations of the contaminants
in the soil whereas the chemical extraction and chemical digestion techniques
result in the determination of the total (adsorbed plus liquid phase) concen-
trations of the contaminants. Whereas the HPPWS technique may be more
appropriate for determination of D*-values from soil concentration profiles,
the chemical extraction and chemical digestion techniques are probably more
suited to determining mass balances. Mass-balance calculations, as well as
several other quality assurance/quality control measures, should be
performed to help evaluate the validity of the test results. Finally, special
precautions should be taken when performing diffusion tests using organic
chemicals due to the volatility and adsorption characteristics of many organic
chemicals.
The major physical factor affecting the value of measure effective diffusion
coefficients is the degree of saturation of the soil, with D*-values for non-
reactive and reactive solutes in saturated soils being as much as 10-20 times
higher than the corresponding values in unsaturated soils. Most other
physical factors only become important in soils which are highly unsaturated.
In addition, the diffusive transport rates of reactive solutes subject to
reversible sorption reactions can be as much as 5000 times lower than those of
nonreactive solutes in saturated soils, and from 20 to 630,000 times lower in
unsaturated soils. However, due to a greater degree of conservatism and
practicality, laboratory diffusion testing in practice likely will be performed
only routinely on saturated soils. As a result, the degree of saturation of the
soil should be a primary consideration in application of the results of
laboratory diffusion tests to the design and evaluation of waste disposal
facilities.
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Journal of Contaminant Hydrology, 7 ( 199 I) 177-217 177

Elsevier Science Publishers B.V., Amsterdam

Laboratory diffusion testing for waste d i s p o s a l -

0169-7722/91/$03.50 © 1991 - - Elsevier Science Publishers B.V.

A cross-sectional area of soil

* M, L and T in brackets [ ] designate dimensions where M is mass, L is length and T is time.

where L is the straight-line, macroscopic distance between two points defining

Effective diffusion coefficients

There currently are no satisfactory methods for determining independently

Fick's first law is as follows:

The transient transport of a chemical species through a representative

~c/~t = (D*/Rd)'O2c/Ox 2 - (vs/Rd)'dc/Ox (11)

As the seepage velocity is reduced, diffusion becomes more significant

F o r m s o f F i c k ' s s e c o n d l a w for d i f f u s i o n in a s a t u r a t e d soil

D e f i n i t i o n o f D* Definition of Adsorption Form of Fick's

c' no Oc'/Ot = D*'O2c'/Ox 2

c yes c~c/Ot = (D*/Rd).~2c/#x 2

c' yes ~c'/~t = (D*/Rd)'t~2c'/~x 2

D ozn c no Oc/Ot = (D*/n)'O 2c/Ox 2

c' no Oc'/Ot = (D*/n)'~2c'/~x 2

c yes Oc/Ot = (D*/nRo)'O 2c/ox 2

c' yes Oc'/Ot = (D*/nRd)'O2 c'/Ox 2

Several other expressions for Fick's second law of diffusion, summarized in

and D* is known as the "apparent diffusion coefficient" whereas Ds is known

Types of diffusion coefficients

or containment are illustrated in Fig. 1. In these cases, the concentrations of

Significance of diffusion in waste disposal

As a result of the above considerations, it is of interest to evaluate when

In general, methods used to measure effective diffusion coefficients of

The steady-state method

The steady-state method for determining D*-values has been used by

Advantages and disadvantages of the steady-state method

and cl is the concentration in the source reservoir (Fig. 2a), which is

Advantage and disadvantage of the time-lag method

In general, transient methods utilize solutions either to eq. 10 or eq. 11

Constant source concentration

Influent With Constant

Effluent: Sampled for

~,~ ,... 0.5 .....................................

through curves, or relative concentration, C/Covs. time or pore volumes of flow

coC - - ,'W-.', erfc

Decreasing source concentration

"; ~-- - - - I Initial Concentration, c

t h r o u g h the soil, the concentrations of the specified chemical species decrease

Advantages and disadvantages of column methods

require the determination of the existence and magnitude of an effective

The half-cell method is illustrated in Fig. 5. In the half-cell method, two

e(x= --~, t > O) = co (25)

and the solution is (Crank, 1975):

BEFORE CONNECTING ( ~1) AFTER CONNECTING

c(x<~O, t=O) = Co; c(x>O, t=O) = 0

and the solution is (Barrer, 1951; Carslaw and Jaeger, 1959):

where A is the cross-sectional area of the soil sample.

Jo = -D*n -~x x=0 = 2 ~/ ~ (30)

When eq. 30 is substituted into eq. 29 and rearranged, an explicit expression

Advantages and disadvantages of the half-cell method

Double reservoir method

Initial Concentration, Co,

to < t1 < t2 < t3

Advantages and disadvantages of the double reservoir method

Single reservoir methods

Constant source concentration The concentration profiles resulting from a

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