Analytical Calculation of Adsorpton Profiles in Uniform Beds.

INTERNATIONAL JOURNAL FOR NUMERICAL AND ANALYTICAL METHODS IN GEOMECHANICS
Int. J. Numer. Anal. Meth. Geomech., 23, 853}879 (1999)
ANALYTIC SOLUTIONS TO THE ADVECTIVE

CONTAMINANT TRANSPORT EQUATION WITH
NON-LINEAR SORPTION
DAICHAO SHENG AND DAVID W. SMITH*

Department of Civil, Surveying and Environmental Engineering, The University of Newcastle, Callaghan, NSW 2300 Australia
SUMMARY
This paper considers advective transport of a soluble contaminant through saturated soil with non-linear
sorption of the contaminant onto a stationary porous media. The non-linear sorption isotherms considered
in the transport analysis are the Langmuir and Freundlich sorption isotherms. A special case of the
Freundlich sorption isotherm is the linear sorption isotherm, and it is shown that in this case transport
through a homogeneous soil results in the initial concentration pro"le simply being translated in the
direction of the groundwater #ow. However, when the sorption isotherm is non-linear the initial concentra-
tion pro"le distorts as it is translated with the groundwater #ow, leading to the development of concentra-
tion shock fronts and rarefactions. Analytic solutions to the non-linear "rst-order hyperbolic equations are
developed for a number of contaminant transport problems of practical signi"cance. It is shown that in the
case of the Langmuir sorption isotherms, shock fronts develop at the leading edge of the concentration
pro"le while for the Freundlich sorption isotherm shock fronts may develop at either the leading or trailing
edge of the concentration pro"le. Copyright 1999 John Wiley & Sons Ltd.
Key words: advective contaminant transport; non-linear analytic solution; shock front
1. INTRODUCTION
Contaminant transport through a porous media is usually mathematically modelled by means of
the dispersion}advection equation. A measure of the relative importance of dispersive trans-
port relative to advective transport is provided by the Peclet number (PN), which is for our
purposes de"ned as,
PN"l¸/D (1)
where l is the average true velocity of the pore #uid within a porous media, D is the coe$cient of
hydrodynamic dispersion, and ¸ is a characteristic length.
When the Peclet number is zero, the dispersion-advection equation reduces to the transient
di!usion equation. An example where this equation "nds application is the analysis of con-
taminant migration beneath an engineered land"ll. On the other hand, when the Peclet number
is very large, advective transport of contaminant dominates hydrodynamic dispersion transport.
*Correspondence to: D. W. Smith Department of Civil, Surveying and Environmental Engineering, The University of
Newcastle, Callaghan, NSW 2308, Australia
CCC 0363}9061/99/090853}27$17.50 Received 24 March 1998

Copyright 1999 John Wiley & Sons, Ltd. Revised 8 June 1998
854 D. SHENG AND D. W. SMITH
While it is an experimental fact that dispersive processes will always accompany advective
transport, for some applications a su$ciently close approximation to contaminant transport
behaviour may be found when dispersive transport is neglected. For example, the advective
transport equation may "nd application when considering contaminant transport through
a uniform aquifer. For this reason, solutions to the non-linear transport equation are of interest in
their own right.
For those cases where both dispersion and advection are of importance, it is often the
advection component that complicates a numerical solution technique. This is due to that the
advective transport equation has a fundamentally di!erent solution compared to the di!usive or
dispersive transport equation. Dispersion or di!usion always tends to smooth the concentration
pro"le while advection maintains or creates discontinuities in the concentration pro"le. Conse-
quently, most e!ective numerical techniques employed for the solution of the dispersion}advec-
tion equation, such as Petrov}Galerkin methods, characteristic-Galerkin methods, upwind
"nite di!erence methods and the Laplace transform methods, have to pay special
attention to the behaviour of the transport equations when advective transport is dominant. For
certain numerical solution techniques such as the Eulerian}Lagrangian "nite element
method an explicit analytic solution of the advective transport equation is required, which
gives an additional motivation to "nd analytic solutions to the non-linear advective transport
equation.
While books and advanced research monographs in applied mathematics do give analytic
solutions to linear advection problems and certain types of non-linear advection problems,\
those solutions cannot be easily extended to non-linear advective problems occurring in relation
to contaminant transport through porous media. For example, a well-known non-linear trans-
port equation is Burger's equation, but the solution to this equation shares little in common to
the advective transport equation with non-linear sorption isotherms which are of interest to
geotechnical and environmental engineers.
In this paper, non-linear sorption isotherms investigated include the Langmuir and Freundlich
sorption isotherms. Two practical boundary value problems encountered in geoenvironmental
engineering are examined in detail. The #uid velocity is assumed to be constant in space and time.
Only one-dimensional solutions will be presented in this paper.
In order to appreciate the e!ects of non-linear sorption during advective transport, it is of
bene"t to "rst review the behaviour of linear sorption during advective transport. This approach
provides a convenient way of introducing the contaminant transport equation, and also provides
reference point with which to compare and contrast later solutions to the advective transport
equation with non-linear sorption.
2. ADVECTIVE CONTAMINANT TRANSPORT WITH LINEAR

SORPTION ISOTHERM
A consideration of mass balance of a contaminant entering and leaving a one-dimensional
Representative Elementary Volume (REV) in a saturated non-deforming porous media leads to
the following well known mass conservation equation:
*f *c
! "n #r (2)
*x *t
Copyright 1999 John Wiley & Sons, Ltd. Int. J. Numer. Anal. Meth. Geomech., 23, 853}879 (1999)
ADVECTIVE CONTAMINANT TRANSPORT EQUATION WITH NON-LINEAR SORPTION 855
where t denotes the time, x the spatial co-ordinate and increases from left to right in this paper,
f the mass #ux of contaminant out of the representative elementary volume, c the concentration
of contaminant in pore #uid, and r the rate of contaminant mass sink per unit volume.
The advective mass #ux is given by
f"nlc (3)
where n is the porosity of the soil, l the average true linear velocity of pore #uid in the soil and
l taken as positive in direction of increasing x.
The mass sink rate may represent sorption of the contaminant onto the solid phase (that is,
onto the soil skeleton). This may be represented by the equation
*S
r"o (4)
*t
where o is the dry density of the soil, and S the mass of contaminant sorbed per unit mass of dry

soil.
Employing equations (3) and (4) in equation (2) and assuming the soil porosity is spatially
invariant leads to the one-dimensional advection transport equation with sorption
*c *c *S
!nl "n #o (5)
*x *t *t
Then employing the chain rule in equation (5) leads to the one-dimensional advective transport
equation with reversible equilibrium controlled sorption, viz,

*c *S *c
!nl " n#o (6)
*x *c *t
In this section we consider the advective transport equation with linear sorption, so in this case
the rate of change of sorbed contaminant with respect to the contaminant concentration is taken
to be constant (see Figure 1), viz,
*S/*c"K (7)

where K is the equilibrium partitioning coe$cient of the contaminant between the #uid and

solid phases, and may be de"ned as the increment in mass of contaminant sorbed onto the soil
skeleton per unit increment of concentration per unit dry mass of soil.
Figure 1. Linear sorption isotherm
Substituting equation (7) into equation (6) leads to the linear advective transport equation:
l *c *c
! " (8)
R *x *t
where R is the retardation coe$cient of the contaminant and R"(1#o K /n).

Equation (8) must be solved subject to a boundary condition and an initial condition which
may be expressed as
c(x, 0)"g(x) (9)
c(0, t)"h(t) (10)
The boundary condition is only needed at the in#ow boundary, here taken to be at x"0 as the
advective velocity is taken to be positive.
The general solution of equation (8) is
c"f (x!lt/R) (11)
where f is an arbitrary function determined by the initial and boundary condition. For a homo-
geneous soil, this solution implies that the concentration pro"le at time zero is unchanged in
shape at later times, and is simply translated to the right as time increases. The moving
contaminant pro"le is sometimes described as a &wave' representing the time-dependent spatial
variation of the contaminant concentration pro"le. The concentration wave moves from left to
right at speed l/R, thereby explaining why R is known as the retardation coe$cient.
If the contaminant moves into another homogeneous soil with a greater linear partitioning
coe$cient, the retardation is increased, the concentration wave is slowed down and is longitudi-
nally compressed. If the contaminant then re-enters a soil with the original sorption properties,
the contaminant wave resumes its original shape and transport speed. This behaviour of the wave
is a characteristic feature of a linear advective transport equation.
Next a zero-order chemical reaction is introduced, representing possible biodegradation of the
contaminant at a rate that is independent of the contaminant concentration. For simplicity it is
assumed that the zero-order rate of reaction is the same for the contaminant in the pore #uid as it
is for the contaminant sorbed onto the solid phase. In this case, the sink term in equation (2)
becomes

*c
r"(n#o K ) #j (12)
*t
where j is the rate constant for the zero-order reaction.

Substituting equations (3) and (12) into equation (2) leads to the following linear advective
transport equation:
l *c *c
! " #j (13)
R *x *t
c"f (x!lt/R)!jt (14)
where f is an arbitrary function again depending on the initial and boundary condition. This
solution implies that the initial contaminant pro"le maintains a similar shape, but diminishes in
size at a constant rate as it is translated to the right at speed l/R.
Now consider the e!ect of a linear "rst-order irreversible reaction, representing possible
radioactive decay, hydrolysis or biodegradation, acting simultaneously with linear reversible
sorption. For simplicity it is assumed that the "rst-order rate of reaction is the same for the
contaminant in the pore #uid as it is for the contaminant sorbed onto the solid phase. In this case,
the sink term in (2) becomes

*c
r"(n#o K ) #jc (15)
*t
where j is the rate constant for the "rst-order reaction.

Substituting equations (3) and (15) into equation (2) leads to the following linear advective
transport equation:
l *c *c
! " #j (16)
R *z *t
c"e\HR f (x!lt/R) (17)
where f is an arbitrary function again depending on the initial and boundary condition. This
solution implies that the initial contaminant pro"le maintains a similar shape over time, but
diminishes in size at an exponential rate as it is translated to the right at speed l/R.
Having considered the behaviour of the concentration pro"le as it is transported by the
groundwater through a saturated homogeneous soil with linear sorption, attention is now turned
to advective transport with non-linear sorption.
3. ADVECTION WITH A NON-LINEAR SORPTION ISOTHERM
3.1. Langmuir sorption isotherm

A well known non-linear sorption isotherm is the Langmuir sorption isotherm shown in
Figure 2. The mathematical equation describing this isotherm can under certain assumptions be
derived from the chemical equilibrium equations, while in other cases it is simply employed as an
approximation of experimental data. In either case, the form of the non-competitive sorption
isotherm is taken to be
BS c
S" (18)
1#Bc
and hence
*S BS
" (19)
*c (1#Bc)
where S is the maximum adsorption capacity, and B is a material constant for a soil-solute

system.
Figure 2. Langmuir sorption isotherm
Substitution of equation (19) into equation (6) leads to the following advective transport
equation:

*c o BS *c
!nl " n# (20)
*x (1#Bc) *t
Again, the solution of equation (20) depends on the boundary and initial condition of the
contaminant concentration, as described by equations (9) and (10). Taken together, equations (9),
(10) and (20) de"ne a non-linear hyperbolic wave propagation problem. The speed of the wave
propagation at concentration c is equal to
dx nl
" (21)

dt o BS
n#
(1#Bc)
It is clear that the speed de"ned by equation (21) is a function of the concentration c, due to the
non-linear sorption term. We can also see that contaminants with a Langmuir sorption isotherm
move more rapidly as the concentration increases. This implies that if the functions g(x) and h(t)
are not equal or constant, regions of higher concentrations will translate to the right at a faster
speed than regions of lower concentration. In pictorial terms, a region of higher concentration
may try to &overtake' a region of lower concentration, leading to the formation of a &shock front'.
A shock front is simply a discontinuity in the concentration pro"le. Alternatively, a region of
higher concentration may &pull away' from a region of lower concentration, leading a &rarefac-
tion'. A rarefaction is simply a region in the concentration wave where the concentration
decreases over time.
The main point of this description of wave behaviour is that unlike the advective transport
equation with linear sorption, the concentration wave distorts as is translated from left to right
(see Figure 3). The distortion in the concentration wave is due to the non-linearity of the sorption
of the contaminant onto the soil skeleton.
Equation (21) de"nes a group of lines in the x}t plane, and along these lines the wave
propagates with a constant concentration. These lines are called characteristic lines or character-
istic directions.
In the following section, two practical problems of advective contaminant transport with
sorption described by the Langmuir isotherm are employed to illustrate the non-linear transport
behaviour. In the "rst case there is a continuous injection of the contaminant from the left
Figure 3. Distortion of a wave pro"le during non-linear transport
boundary at a higher concentration than the initial concentration. This problem illustrates the
behaviour of a concentration &shock front'. In the second case, the injection of contaminant at the
left boundary is maintained for a "nite length of time, then reduces to the initial concentration at
the upstream boundary. This problem illustrates the formation of a rarefaction along the trailing
edge of the concentration wave as it propagates through the soil. It is noted here that in the
following section, the same problems are investigated for contaminant sorption according to
a Freundlich sorption isotherm.
3.1.1. Case I: continuous injection (shock front)

g(x)"a, 0(x(R
h(t)"b, 0)t(R
In this case, the incoming concentration (Figure 4) is larger than the initial concentration and so it
is transported with a higher speed. The transport speed of the incoming concentration b is given
by
dx nl
l" " (22)
@ dt BS
n#o
(1#Bb)
which corresponds to the slope of dashed lines in the plan view of the x}t plane (see Figure 5). The
transport speed of the initial concentration a is given by
dx nl
l" " (23)
? dt BS
n#o
(1#Ba)
which corresponds to the slope of the solid lines in Figure 5. Since the upstream speed l is higher
@
than the downstream speed l , a shock in the concentration will develop (or in this case be
?
maintained). To "nd the speed of the shock front, the following approach may be adopted.
Substituting equation (18) into equation (5) leads to a statement of mass conservation for
a representative elementary volume, viz,
*c *
!nl " F(c) (24)
*x *t
Figure 4. Initial concentration and boundary condition for Case I: Continuous injection
where
BS c
F(c)"nc#o S"nc#o (25)
1#Bc
Equation (24) holds even if c is not a smooth function. Now let,
x"X (t) (26)
Q
denote the location of the shock front (that is, the location of the concentration discontinuity).
The concentration on the left side of X (t) is b and on the right side it is a (see Figure 5).
Q
Integrating equation (24) from x"x to x"x leads to

V *c d V
! nl dx" F(c) dx (27)
*x dt
V V
where x and x are respectively on the left and right side of X (t) at time t. The left-side term of
Q
equation (27) is simply !nl(c(x , t)!c(x , t)"!nl(a!b). The right-side term of equation

(27) can be evaluated using the Leibnitz rule for di!erentiating integrals which shows

d V 6Q R *F(c) dX V *F(c) dX
F(c) dx" dx#F(b) Q# dx!F(a) Q (28)
dt *t dt *t dt
V V 6Q R
Both integrals on the right side of equation (28) tend to zero in the limit as x P X (t)\ and
Q
x P X (t)>. Therefore, equation (27) "nally becomes
Q
dX dX
!nl(a!b)"F(b) Q!F(a) Q (29)
dt dt
Substituting F(a) and F(b) according to equation (25) into equation (29) gives the shock front
speed;
dX nl(b!a) nl
l " Q" " (30)
Q@? dt F(b)!F(a) o BS
n#
(1#Ba)(1#Bb)
where l denotes the speed of a shock front with a concentration step from b to a. The speed of
Q@?
the shock front is intermediate between the speeds l and l . The position of shock front at some
@ ?
time is represented by the enhanced solid line in the x}t plane shown in Figure 5.
Figure 5. Characteristic lines and shock front for Case I: Continuous injection, Langmuir sorption isotherm
For later purposes it is noted here that if the concentrations b and a at the upstream
and downstream sides of a shock front respectively change with time, (30) may be ex-
pressed as
nl
l" (31)
Q o BS
n#
(1#Bc )(1#Bc )

where c is the concentration at the upstream side of the shock front at time t, and c is the

concentration at the downstream side of the shock front at time t.
3.1.2. Case II: Temporary injection (shock front and rarefaction)
g(x)"a, x'0
h(t)"b, 0)t)t

h(t)"a, t't

As for Case I, the shock front at the leading edge of the injected contaminant patch will
be maintained. Once the injection stops, the incoming concentration (Figure 6) will be
smaller than the injected concentration and so will move at a lower speed. Therefore, an area
of rarefaction in concentration will develop (see Figure 7). The length of the rarefaction area
at time t can be determined from the speed di!erence at the downstream and the up-
stream boundary. The upstream speed is l at any time t*t . The downstream speed is l until
? @
a certain time t when the width of the injected concentration patch becomes zero due to the
@
speed di!erence between l and l (see Figure 7 and 8). Therefore, the length of the rare-
@ Q@?
faction area before t is the distance from l (t!t ) to l (t!t ). After time t , the downstream
@ ? @ @
speed of the rarefaction area will be the speed of the shock front which gradually decreases
from l at t to l at in"nite time. The length of the rarefaction area will be the distance from
Q@? @ ?
l (t!t ) to l (t!t ), where l is the speed of the shock front with a concentration step from
? QA? QA?
c(x, t) to a (see Figure 7). The concentration c(x, t) in the rarefaction area can be determined as
follows.
Figure 6. Initial concentration and boundary condition for Case II: Temporary injection
In the rarefaction area, the contaminant transports with a velocity l along the characteristic
A
lines determined by the concentration c and so the distance travelled is given by
nl(t!t )
x"l (t!t )" , R (t))x)R (t) (32)
A o BS
n#
(1#Bc)
where R (t) is the &upstream' boundary of the rarefaction area, and R (t) is the &downstream'

boundary of the rarefaction area.
For the case shown in Figure 7, R (t) is given by l (t!t ) and R (t) by l (t!t ) for t)t and
? @ @
by X (t) for t't . Equation (32) can be solved for c in terms of x and t:
Q @

1 o BS x 1
c(x, t)" ! , R (t))x)R (t) (33)
B nl(t!t )!nx B

Equation (33) shows that the concentration in the rarefaction area is not a linear function of x.
The time t after which the upstream concentration at the shock front will be less than the
@
injected concentration b can be deduced from the geometry of characteristic lines shown in Figure
7. The initial patch width at time t is l t , and the speed di!erence between the shock front and
Q@?
the patch is l !l . Therefore, the time taken before the upstream concentration at the shock
@ Q@?
front is reduced from the injected concentration b is equal to
l t
t "t # Q@? (34)
@ (l !l )
@ Q@?
where the speeds l and l are determined according to equations (22) and (30), respectively.
@ Q@?
The shock front X (t) is a straight line de"ned by X "l t for t)t in the x}t plane, but
Q Q Q@? @
curves for t't . The curve of the shock front trajectory in the x}t plane arises because of the
@
decrease in speed of the shock front as the maximum concentration in the shock front decreases.
To determine the location of X (t) for t't , it is necessary to solve the following integral
Q @
equation:

6Q o BS c o BS a
nc# ! na# dx"nl(b!a)t (35)
1#Bc 1#Ba
J? R\R
Figure 7. Characteristic lines, shock front and rarefaction area for Case II: Temporary injection, Langmuir sorption
isotherm
Equation (35) states that the total mass within the rerefaction area minus the initial mass in this
area must equal the injected mass. The concentration c in equation (35) can be replaced by
equation (33). The solution of (35) for X (t) is given in Appendix I. With an explicit expression of
Q
X (t), it is possible to determine the time when the maximum concentration is reduced to a certain
Q
value, for example, to half the injected concentration (this is, b/2).
The solution for the case of temporary injection of a contaminant transport through a soil with
a Langmuir sorption isotherm (18) is shown pictorially in Figure 8. This "gure clearly illustrates
the development of the rerefaction area on the trailing edge of the concentration wave, and the
changing trajectory of the shock front in the x}t plane as the maximum concentration in the
shock front decreases with time.
3.2. Freundlich sorption isotherm

The Freundlich sorption isotherm sometimes provides a good approximation to the experi-
mental data for contaminant sorption isotherms. The general form of the Freundlich sorption
isotherm is (see Figure 9),
S"K cK (36)

and so in this case,
*S/*c"K mcK\ (37)

where K and m is a material constant for a soil}solute system.

Substitution of equation (37) into equation (6) leads to the following governing advective
transport equation:
*c *c
!nl "(n#o K mcK\) (38)
*x *t
Figure 10. Rarefaction area and shock front in concentration for Freundlich sorption isotherm in Case I: Continuous
injection, (a) m'1, (b) m(1
pro"le. For m'1, a rarefaction develops at the leading edge of the concentration pro"le and so
an initial discontinuity in the concentration pro"le will be smoothed with time, as illustrated
using characteristics in Figure 10(a). If m(1, a shock front develops and so an initially smooth
concentration pro"le will develop a discontinuity in concentration at the leading edge, as
illustrated using characteristics in Figure 10(b).
The speed of the injected concentration b is given by
dx nl
l" " (40)
@ dt n#o K mbK\

which corresponds to the slope of dashed lines in Figure 10. The transport speed of the initial
concentration a is given by
dx nl
l" " (41)
? dt n#o K maK\

which corresponds to the slope of the solid lines in Figure 10.
The rarefaction area in Figure 10(a) at time t is the distance from l t to l t. A concentration c in
@ ?
this rarefaction interval transports with a speed l so that
A
nlt
x"l t" , l t)x)l t (42)
A n#o K maK\ @ ?

This equation can be solved explicitly for c in terms of x and t as

nlt!nx K\
c(x, t)" , l t)x)l t (43)
o K mx @ ?

The location of the shock front in Figure 10(b) can be determined in a similar way to that for the
shock front shown in Figure 5 (for the Langmuir sorption isotherm), viz,
dX nl(b!a) nl(b!a)
l " Q" " (44)
Q@? dt F(b)!F(a) n(b!a)#o K (bK!aK)

Figure 10. Rarefaction area and shock front in concentration for Freundlich sorption isotherm in Case I: Continuous
injection, (a) m'1, (b) m(1
pro"le. For m'1, a rarefaction develops at the leading edge of the concentration pro"le and so
an initial discontinuity in the concentration pro"le will be smoothed with time, as illustrated
using characteristics in Figure 10(a). If m(1, a shock front develops and so an initially smooth
concentration pro"le will develop a discontinuity in concentration at the leading edge, as
illustrated using characteristics in Figure 10(b).
The speed of the injected concentration b is given by
dx nl
l" " (40)
@ dt n#o K mbK\

which corresponds to the slope of dashed lines in Figure 10. The transport speed of the initial
concentration a is given by
dx nl
l" " (41)
? dt n#o K maK\

which corresponds to the slope of the solid lines in Figure 10.
The rarefaction area in Figure 10(a) at time t is the distance from l t to l t. A concentration c in
@ ?
this rarefaction interval transports with a speed l so that
A
nlt
x"l t" , l t)x)l t (42)
A n#o K maK\ @ ?

This equation can be solved explicitly for c in terms of x and t as

nlt!nx K\
c(x, t)" , l t)x)l t (43)
o K mx @ ?

The location of the shock front in Figure 10(b) can be determined in a similar way to that for the
shock front shown in Figure 5 (for the Langmuir sorption isotherm), viz,
dX nl(b!a) nl(b!a)
l " Q" " (44)
Q@? dt F(b)!F(a) n(b!a)#o K (bK!aK)

Figure 11. Characteristic lines, shock front and rarefaction area for Case II: Temporary injection, Freundlich sorption
isotherm with m'1
3.2.2. Case II: Temporary injection. As for the example of continuous injection, two di!erent
wave pro"les can develop, dependent on the value of m. For m(1, the injected concentration
patch will move in a similar way to that shown in Figures 7 and 8, except that the downstream
shock front will have a speed de"ned by equation (44) and the concentration in the upstream
rarefaction area will be de"ned by equation (43) with time t starting from the end of injection t .

Perhaps unexpectedly, for m'1, the shock front will develop at the upstream side of the
injected concentration patch whereas a rarefaction area will develop at the downstream side of
the patch (as we have seen in Case I). For time t before t (see Figure 11 for de"nition of t ), the
@ @
location of the shock front in the x}t plane is given by
nl(b!a)(t!t )
x"X (t)"l (t!t )" (45)
Q Q@? n(b!a)#o K (bK!aK)

After time t , the speed of the shock front will gradually increase from l at t to l as time
@ Q@? @ ?
becomes in"nitely large. An explicit function for the location of this shock front is given in
Appendices II and III. The time t can be computed using equation (34) with l and l deter-
@ @ Q@?
mined according to (40) and (44), respectively.
The rarefaction area is the distance from l t to l t for t)t and from X (t) to l t for t't . The
@ ? @ Q ? @
concentration in the rarefaction area is determined by equation (43). The characteristic lines as
well as the location of the shock front and the rarefaction area are shown in Figure 11. The
analytic solution of this example problem is pictorially illustrated in Figure 12.
4. EFFECTS OF IRREVERSIBLE REACTION
4.1. Zero-order reaction

The governing equation for advective transport with a simultaneous zero-order chemical
reaction is given by equation (12), viz,

*c *S *c
!nl " n#o #j (46)
*x *c *t
Figure 12. Schematic view of solution of Case II: Temporary injection: Freundlich sorption isotherm
where j is a constant representing the rate of reaction. Along the characteristic directions de"ned
by
dx nl
" (47)

dt *S
n#o
*c
the partial di!erential equation (46) reduces to

dc *c dx *c *c *c
nl
" # " # "!j (48)

dt *x dt *t *x *S *t
n#o
*c
Equation (48) indicates that along its characteristic directions de"ned by equation (47), the
unknown concentration c is a linear function of time t, viz,
c"!jt#c (49)

where c is the initial concentration at t"0. From equation (49), it is apparent that a concentra-

tion wave transports along its characteristic direction with a linearly decreasing amplitude over
time, since j is usually a positive number. For a non-linear sorption isotherm, the characteristic
directions dx/dt are in general functions of c, and so these directions change as c changes during
the transport process. This means that (47) de"nes a group of curved characteristics, instead of
straight lines as was the case when there was no chemical reaction. The explicit expressions of
characteristic curves for a Langmuir isotherm can be found by substituting (49) into (47) and
integrating with respect to time. This leads to

oS l jB (no BS t
x"lt! arctan #m (50)
nB j o BS #n(1#Bc )(1#Bc !jBt)

where m is an arbitrary x position when t"0.
Figure 13. E!ect of zero order reaction on the concentration transport, uniform concentration
For the Freundlich sorption isotherm a general explicit form describing the characteristic
curves for any value of m cannot be obtained analytically, so an example solution is given for
m"2. For this case,
nl
x" (ln(n#2o K c )!ln(n#2o K c !2o jK t))#m (51)
2o jK

The distances de"ned by equation (50) and (51) are relatively complicated functions of t, which
makes the solution of equation (46) more complex than discussed in the previous section. In the
simplest case when the initial concentration c is uniform for !R(x(R, the solution of

equation (46) is an inclined surface in the three-dimensional space as shown in Figure 13. At
a certain time t , the initial concentration c will decrease to zero and the contaminant will have
Q
disappeared. This time is given by,
t "c /j . !R(x(R (52)
Q
However, if the initial concentration is not uniform or a di!erent concentration is applied at
a boundary, shocks and rarefactions in concentration pro"le can in general develop and the
solutions to equation (46) are much more complex than that shown in Figure 13.
To illustrate the solution of equation (46), the same example problems of continuous and
temporary injection will be employed again, but now the initial concentration will be set to zero
for the sake of simplicity (i.e. c(x, 0)"g(x)"0).
4.1.1. Case I: Continuous injection. For a Langmuir sorption isotherm, the speed of concentra-
tion transport increases with increasing concentration. Therefore, at the front of the injected
concentration patch, the upstream speed is higher than the downstream speed and a shock front
will develop (or be maintained). The speed of the shock front can be calculated from (31), with
c "0 and c "b!jt, viz,

dX nl nl
v " Q" " (53)
Q dt o BS o BS
n# n#
(1#Bc )(1#Bc ) (1#Bb!Bjt)

Figure 14. Schematic view of solution of Case I: Continuous injection, Langmuir sorption isotherm and Freundlich
sorption isotherm with m"2, Zero-order reaction
Integrating (53) gives the explicit expression of the shock front
o S l n#nBb#o BS !nBjt
X "lt# ln (54)
Q nj n#nBb#o BS

The concentration c decreases linearly from c"b at x"0 to c"b!jt at position X . The
Q
solution is illustrated in Figure 14. At time t "b/j, the concentration at X decreases to zero and
Q Q
the shock front disappears. This location where the shock front disappears can be found by
substituting t with b/j in equation (54), viz,
lb o S l n#o BS
X " # ln (55)
Q j nj n#nBb#o BS

For the contaminant sorption onto the soil skeleton described by the Freundlich sorption
isotherm, with a particular value of m chosen for simplicity (that is m"2), the speed of the shock
front is given by
dX nl(c !c ) nl
l " Q" " (56)
Q dt n(c !c )#o K (cK!cK ) n#o K (b!jt)

and so the shock front location is given by

n l j (no K t
X" arctan (57)
Q oK j n#o K b(b!jt)

As shown pictorially in Figure 14, the solution of equation (46) for the Freundlich sorption
isotherm with m"2 is similar to that for the Langmuir sorption isotherm. The position x where
Q
the concentration decreases to zero and the shock front disappears (see Figure 14) can again be
found by substituting b/j for t in equation (57).
Figure 15. Schematic view of solution case II: Temporary injection, Langmuir sorption isotherm or Freundlich sorption
istherm with m'1, Zero-order reaction
4.1.2. Case II: Temporary injection. For a Langmuir sorption isotherm or a Freundlich
sorption with m'1, the solution of equation (46) for a temporary injection of contaminant is
schematically shown in Figure 15. The time t (shown in Figure 15) is once again the time when

the maximum concentration in the shock front is reduced by the rarefaction. For time t(t the
@
location of the shock front location, X (t), is de"ned by equations (54) and (57) for the Langmuir
Q
and Freundlich sorption isotherm respectively. For time t't , the location of the shock front,
@
X (t), will be a complicated function of t.
Q
Explicit expressions of the concentration in the rarefaction area can be obtained by solving
equations (50) or (51) for c in terms of x and t and then substituting c (x, t) into equation (49).

This leads to
c(x, t)"
1
2
jt#
for the Langmuir sorption isotherm and to

oS

Bn
tan

(lt!x)j
l
4jt

oS

Bn
!jt !
B
1
(58)
jt n
c(x, t)" ! (59)

2jK x 2K
exp !1
nl
for the Freundlich sorption isotherm with m"2.

The time t can be found by solving for the crossing point in the x}t plane between the shock
@
front X and the characteristic curve through the point (x"0, t"t ). Unfortunately the explicit
Q
expressions for t are too complex to be presented in this paper. Once t is known, the maximum
@ @
concentration at t is then given by
@
c (t )"Max(b!jt ,0) (60)
@ @
4.2. First-order reaction

The governing equation for the advective transport with a "rst-order reaction takes the form

*c *S *c
!nl " n#o #jc (61)
*x *c *t
Along the characteristic directions de"ned by
dx nl
" (62)

dt *S
n#o
*c
the partial di!erential equation (46) reduces to
dc *c dx *c *c nl *c
" # " # "!jc (63)

dt *x dt *t *x *S *t
n#o
*c
This indicates that along its characteristic directions, the unknown concentration c is an
exponential function of time t, viz,
c"c exp(!jt) (64)

where c is the initial concentration at t"0.

The characteristics de"ned by equation (61) for a Langmuir or a Freundlich sorption isotherm
are in general complex non-linear functions of t and explicit expressions cannot be obtained
easily. However, the e!ect of the "rst-order reaction on the advective transport is much the same
as for the zero-order reaction, but with an exponential decay rate. The solution of equation (61),
for the case of a temporary contaminant injection, is shown pictorially in Figure 16.
5. NUMERICAL EXAMPLE
A simple problem of practical signi"cance to environmental engineers interested in predicting the
development of a contaminant plume is described here. Fluoride contaminated waste is place in
an unlined pit and is migrating vertically through an initially uncontaminated clayey sand to an
underlying aquifer (see Figure 17). The amount of #uoride waste in the pit is taken to be
su$ciently large so that the leachate from the unlined pit has essentially a constant concentration
of #uoride, taken to be 300 mg/l. An important problem is to estimate the time for the #uoride
contaminant to move from the unlined pit to the aquifer below.
The properties of the clayey sand between the pit and the aquifer are taken to be,
Dry density o "1500;10 mg/l

Porosity n"0)44
Permeability k"10\ m/s
Experimental investigations using batch testing and di!usion cells have established that the
sorption isotherm for #uoride onto kaolinite is of a competitive Langmuir type, and the
amount of sorption is strongly dependent on pH values (see Figure 18). The competitive sorption
Figure 16. Schematic view of solution of Case II: Temporary injection, Langmuir sorption isotherm or Freundlich
sorption isotherm with m'1, First-order reaction
Figure 17. Advective transport of #uoride contaminant from an unlined pit to an undelrying aquifer
Figure 18. Fluoride sorption isotherms in kaolinite, Kau (1997)
isotherm is described by the equation
S B c
S" (65)
1#B 10&\#B c

where
S "3)33 mg/g (for 100% kaolinite)

B "0)0216 l/mg

B "8)05

It is assumed that the sorption of the #uoride onto the sand is purely due to clay content
(S "0)333 mg/l, for 10 per cent kaolinite content), and that the pH of the leachate does not vary

with depth. The e!ective dispersion coe$cient of the soil varies between 10\ and 10\ m/s,
which gives a Peclet number in the range of 20}20 000, with reference to l in equation (67) and
a characteristic length of 5 m. Due to the relatively large Peclet number, the transport process will
be advection dominated, and so a good estimation of the transport time to the aquifer for
di!erent pH's may be made using the non-linear advective transport solutions developed in
previous sections.
Substituting equation (65) into equation (25) and then into equation (30) shows the transport
speed of the #uoride front from the unlined pit is given by
dX nl(b!a) nl
l " Q" " (66)
Q@? dt F(b)!F(a) o B S (1#B 10&\)
n#
(1#B 10&\#B a)(1#B 10&\#B b)

The average true downward velocity of the pore #uid within the clayey sand is, according to the
Darcy law
l 1 *H 10\ 10
l" " k " "0)45;10\ m/s (67)
n n *t 0)44 5
and employing this result in equation (66) leads to the transport speed of the #uoride front
nl 2;10\
l " " (68)
Q?@ oS B 1)079;10
n# 0)44#
1#B 10&\#B b 7)48#8)08;10&\

Therefore, the time for the #uoride contaminant to reach the aquifer is given by

5 1)079;10
t" "2)5;10 0)44# (69)
l 7)48#8)08;10&\
Q?@
The time calculated for various pH values using equation (69) is shown in Figure 19, identi"ed by
the legend &non-linear'.
It is of interest to compare the non-linear solution given by equation (69) with a solution for
a linear sorption isotherm. One approach to linearize the sorption isotherm would be to use the
initial tangential slope of the S}c curve (K ) to approximate the derivative *S/*c (see Figure 18).

For this approach

*S S B (1#B ;10&\) S B
K " " " (70)
*c (1#B ;10&\#B c) 1#B 10&\
A A
Figure 19. Time for #uoride arrival at the aquifer versus pH (Non-linear; using non-linear sorption isotherm, Linear:
using linear sorption approximated by the initial tengantial slope K )

and the transport speed of the #uoride contaminant through the clayey sand is given by
nl
l"
A n#o K

The time for the #uoride contaminant to reach the aquifer would therefore be (see Figure 19).

5 1)079;10
t" "2)5;10 0)44# (71)
l 1#8)08;10&\
A
Comparing the two plots in Figure 19 it is clear that using the initial tangent sorption isotherm
leads to signi"cant larger estimated transport times compared to the non-linear transport
predictions, particularly at low pH values. At high pH values the non-linear and linear solutions
converge due to sorption of the contaminant onto the soil skeleton reducing to zero.
An alternative linear approximation of equation (65) is to use the secant slope (K ) for *S/*c

(see Figure 18). The linear sorption isotherm is then given by
S B
K " (72)
1#B 10&\#B b

and the transport speed of the #uoride contaminant through the clayey sand is
nl
l" (73)
A oS B
n#
1#B 10&\#B b

Equation (73) predicts exactly the same shock front speed l as given by equation (68) for the
Q?@
non-linear sorption isotherm. Therefore, in this example, this simple secant linear approximation
leads to the exact solution. It is cautioned that this coincidence of solutions would not necessarily
follow for more complicated initial and boundary conditions.
6. CONCLUSION
In this paper, analytic solutions to the advective transport equation with non-sorption has been
developed for a several contaminant transport problems of practical signi"cance. It has been
shown that advective transport of a contaminant in a porous media with non-linear sorption
isotherm is a complex process. A number of important behaviours may be observed, namely,
(1) When an initially continuous contaminant concentration pro"le is transported through
a porous media with a non-linear sorption isotherm, concentration shocks and rarefactions
may develop.
(2) The transport speed of a concentration shock front is intermediate between the transport
speed of the concentration at its downstream and upstream sides.
(3) In the case of the Langmuir sorption isotherm, a shock front may develop at the leading
edge of the concentration pro"le and a rarefaction area may develop at the trailing edge.
(4) For the Freundlich sorption isotherm, shock fronts and rarefaction areas may develop at
either the leading or trailing edges of the concentration pro"le, depending on the value of
the material parameter m.
It has been demonstrated by the solution of a simple problem that the analytic solutions
presented in this paper can be employed to solve contaminant transport problems of practical
interest. Finally, it is expected that the analytic solutions presented in this paper may also be
employed in the future development of more accurate numerical techniques of the non-linear
dispersion-advection transport equation.
NOTATION
a initial concentration
B coe$cient in Langmuir sorption isotherm
b injected concentration
c concentration in pore #uid
D coe$cient of hydrodynamic dispersion
f mass #ux of contaminant out of the representative elementary volume
K distribution coe$cient in a linear sorption isotherm

K material parameter in Freundlich sorption isotherm

¸ characteristic length
m material parameter in Freundlich sorption isotherm
n soil porosity
PN Peclet number
R retardation coe$cient
R downstream boundary of rarefaction area

R upstream boundary of rarefaction area

r rate of contaminant mass sink per unit volume
S sorbed concentration
S maximum sorption capacity in Langmuir sorption isotherm

t time
t time at which the width of the injected concentration patch becomes zero

t end time of injection

l average true velocity of pore #uid
l transport speed of concentration a
?
l transport speed of concentration b
@
l transport speed of concentration c
A
l transport speed of shock front s
Q
l transport speed of shock front with a concentration step from b to a
Q@?
X shock front location
Q
x space coordinate
o soil dry density

j rate constant of reaction
APPENDIX
A.1. Location of shock front in the case of temporary injection with a Langmuir sorption isotherm
For t)t , the shock front location X (t) is a straight line de"ned by
@ Q
nlt
X "l t" , t)t (74)
Q Q@? o BS @
n#
(1#Ba)(1#Bb)
Fo t't , the shock front will curve gradually in the x}t plane from speed l at t to speed l at
@ Q@? @ ?
time in"nity. To "nd the location of X (t) for t't , mass balance considerations indicate that the
Q @
total mass within the rarefaction area minus the initial mass in this area must equal the injected
mass, viz,

6Q o BS c o BS a
nc# dx! na# (X !l (t!t ))"nl(b!a)t (75)
1#Bc 1#Ba Q ?
J R\R
? G
The concentration c in (75) can now be replaced according to (33). Integrating the "rst term on the
left-hand side of (75) leads to, after some rearrangement
1
X" (Al(t!t )!2A A (t!t )#2A A )
Q 2(A#A )

1
# (A (t!t )#A (t!t )#A , t't (76)
2(A#A ) @

where

no S
A "2
B
n o S Ba
A "o S ! !na!
B 1#Ba
A "nl(b!a)t

A "A ((l!l )l !A l
? ? ?
A "Al!4AA A l!4AA

A "4AA A #8AA A #2AA A l

A "!4AA

With this explicit expression of X (t), it is possible to determine the time when the maximum
Q
concentration is reduced to a certain value, for example, to b/2.
A.2. Location of shock front in case of temporary injection with a Freundlich sorption isotherm
(m"0.5)
For the Freundlich sorption isotherm, equation (36), when m(1, the injected concentration
patch will distort in a similar way to that for the Langmuir sorption isotherm, i.e. a shcok front
forms at the downstream side and rarefaction area develops at the upstream side of the injected
concentration patch. The characteristic lines and the pictorial depiction of the solution are similar
to those shown in Figure 7 and 8, respectively. The shock front location for t)t is a straight line
@
given by
nl(b!a)t
X "l t" (77)
Q Q@? n (b!a)#o K (bK!aK)

while for t't the shock front location will curve due to the decreasing concentration at the
@
upstream side of the front. Applying the principle of mass balance in the rarefaction area leads to
the following integral equation:

6Q
(nc#o K cK) dx!(n a#o K aK)(X !l (t!t ))"nl(b!a)t (78)
Q ?
J? R\RG
The concentration c in equation (75) is the concentration within the rarefaction area which is
given by equation (43) with t replaced by (t!t ), i.e.

nl(t!t )!nx K\
c(x, t)" , l (t!t ))x)l (t!t ) (79)
o K mx @ ?

Substituting equation (79) into equation (78) leads to an implicit equation for X . For a given m,
Q
the integral equation (78) can be solved explicitly for X . For example, for m"0)5, the shock front
Q
X is de"ned by
Q
1
X" (!A (t!t )!A #(A A (t!t )#A ), t't (80)
Q 2A @

where

a oK
A " n#
n 2(a

oK
A "!2al n#
2(a
A "n(b!a)lt

n#o K
A "4ao K l
n
A.3. Location of shock front in the case of temporary injection with a Freundlich sorption isotherm
(m"2)
For Freundlich sorption isotherm with m'1, a shock front will develop at the upstream side
of the injected concentration patch whereas a rarefaction area will develop at the downstream
side of the injected concentration patch. For time t before t in Figure 11, the location of the shock
@
front is a line in the x}t plane by
nl(b!a)(t!t )
X (t)"l (t!t )" (81)
Q Q@? n(b!a)#o K (bK!aK)

After time t , the location of the shock front is de"ned by the mass balance equation,
@

J?R
(nc#o K cK) dx!(na#o K aK)(X !l t)"nl(b!a)t (82)
Q ?
6Q
where c is given by (43). Equation (82) implicitly de"nes X in terms of t. For a given m, the
Q
integral in (82) can be solved for X . For example, for m"2, the shock front location X is
Q Q
explicitly de"ned by
1
X" (A t#A #(A A t#A ), t't (83)
Q 2A @

where
(n#2o K a)
A "
4o K

nl(n#2o K a)
A "
2o K

A "n(b!a)lt

REFERENCES
1. J. Bear, Dynamics of Fluids in Porous Media, Elsevier, New York, 1972.
2. M. T. van Genuchten, &Recent progress in modelling water #ow and chemical transport in the unsaturated zone', Proc.
20th General Assembly of the International ;nion of Geodesy and Geophysics, Vienna, Austria, IAHS, Institute of
Hydrology, Wallingford, UK, 1991, pp. 169}183.
3. R. K. Rowe, R. M. Quigley and J. R. Booker, in E. F. N. Spon (ed.), Clayey Barrier Systems for =aste Disposal
Facilities, Chapman & Hall, London, 1985.
4. C. Zheng and G. D. Bennet, Applied Contaminant ¹ransport Modelling: ¹heory and Practice, Van Nostrand Reinhold,
New York, 1995.
5. I. Christie, F. Gri$ths, A. R. Mitchell and O. C. Zienkiewicz, &Finite element methods for second order di!erential
equations with signi"cant "rst derivatives', Int. J. Numer. Meth. Engng., 10, 1389}1396 (1976).
6. A. N. Brooks and T. J. R. Hughes, &Streamline upwind/Petrov-Galerkin formulation for convection dominated #ows
with particular emphasis on the incompressible Navier Stokes equation', Comp. Meth. Appl. Mech. Engng., 32,
199}259 (1982).
7. R. A. Adey and C. A. Brebbia &Finite element solution of e%uent dispersion', in (eds) C. A. Breddia and J. J. Connor
Numerical Methods in Fluid Mechanics Pentech Press, Southampton, 1974, pp. 325}354.
8. J. Douglas and T. F. Russell &Numerical methods for convection dominated di!usion problems based on combining
the method of characteristics with "nite element or "nite di!erence procedures', SIAM J. Numer. Anal., 19, 871}885
(1982).
9. R. K. Rowe and J. R. Booker, &A "nite layer techniques for calculating three dimensional pollutant migration in soil',
Geotechnique, 36, 205}214 (1986).
10. E. A. Sudicky, &The Laplace transform Galerkin technique, A time continuous "nite element theory and application to
mass transport in groundwater', =ater Resour. Res., 25, 1833}1846 (1989).
11. R. Courant, E. Isaacson and R. Rees, &On the solution of non-linear hyperbolic di!erential equations by "nite
di!erences', Comm. Pure Appl. Math., V, 243}255 (1952).
12. D. B. Spalding, &A novel "nite di!erence formulation for di!erential equations involving both "rst and second
derivatives', Int. J. Numer. Meth. Engng., 4, 551}559 (1972).
13. S. P. Neuman, &Adaptive Eulerian-Lagrangian "nite element method for the advection dispersion', Int. J. Numer.
Meth. Engng., 20, 321}337 (1984).
14. D. Sheng and K. Axelsson, &Uncoupling of coupled #ows in soil, A "nite element method', Int. J. Numer. Anal. Meth.
Geomech., 19, 537}553 (1995).
15. J. D. Logan, Applied Mathematics, A Contemporary Approach, Wiley, New York, 1987.
16. J. Smoller, Shock =aves and Reaction}Di+usion Equations, Springer, New York, 1983.
17. R. Courant and D. Hilbert, Methods of Mathematical Physics, Vol. II, Wiley-Intersience, New York, 1962.
18. R. H. Freeze and J. A. Cherry, Groundwater, Prentice-Hall, Englewood Cli!s, NJ, 1979.
19. P. M. H. Kau, &The experimental investigation of #uoride migration in clay soils', Ph.D. ¹hesis, University of
Newcastle, Australia, 1997.
20. W. A. Jury, W. R. Gardner and W. H. Gardner, Soil Physics, 5th edn, Wiley, New York, 1991.

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INTERNATIONAL JOURNAL FOR NUMERICAL AND ANALYTICAL METHODS IN GEOMECHANICS

Int. J. Numer. Anal. Meth. Geomech., 23, 853}879 (1999)

ANALYTIC SOLUTIONS TO THE ADVECTIVE

DAICHAO SHENG AND DAVID W. SMITH*

CCC 0363}9061/99/090853}27$17.50 Received 24 March 1998

2. ADVECTIVE CONTAMINANT TRANSPORT WITH LINEAR

Figure 1. Linear sorption isotherm

where R is the retardation coe$cient of the contaminant and R"(1#o K /n).

c(0, t)"h(t) (10)

c"f (x!lt/R) (11)

where j is the rate constant for the zero-order reaction.

The general solution of equation (13) is

c"f (x!lt/R)!jt (14)

where j is the rate constant for the "rst-order reaction.

3. ADVECTION WITH A NON-LINEAR SORPTION ISOTHERM

3.1. Langmuir sorption isotherm

Figure 2. Langmuir sorption isotherm

Figure 3. Distortion of a wave pro"le during non-linear transport

3.1.1. Case I: continuous injection (shock front)

3.1.2. Case II: Temporary injection (shock front and rarefaction)

3.2. Freundlich sorption isotherm

4. EFFECTS OF IRREVERSIBLE REACTION

4.1. Zero-order reaction

the partial di!erential equation (46) reduces to

Integrating (53) gives the explicit expression of the shock front

for the Langmuir sorption isotherm and to

for the Freundlich sorption isotherm with m"2.

4.2. First-order reaction

Figure 18. Fluoride sorption isotherms in kaolinite, Kau (1997)

isotherm is described by the equation

S "3)33 mg/g (for 100% kaolinite)

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Figure 18. Fluoride sorption isotherms in kaolinite, Kau (1997)