Journal of Hydrology, 73 (1984) 227--258 227

Elsevier Science Publishers B.V., Amsterdam -- Printed in The Netherlands

[21

NONEQUILIBRIUM AND EQUILIBRIUM SORPTION WITH A LINEAR

S O R P T I O N ISOTHERM D U R I N G MASS T R A N S P O R T T H R O U G H AN
I N F I N I T E P O R O U S M E D I U M : SOME A N A L Y T I C A L S O L U T I O N S

C.L. CARNAHAN and J.S. REMER

Earth Sciences Division, Lawrence Berkeley Laboratory, University of California,
Berkeley, CA 94720 (U.S.A.)
(Received April 1, 1983;revised and accepted January 9, 1984)

ABSTRACT

Carnahan, C.L. and Remer, J.S., 1984. Nonequilibrium and equilibrium sorption with
a linear sorption isotherm during mass transport through an infinite porous medium:
some analytical solutions. J. Hydrol., 73: 227--258.

Analytical solutions have been developed for the three-dimensional axisymmetric

problem of solute transport in a steady field of groundwater flow with nonequilibrium
mass transfer of a radioactive species between fluid and solid phases, and with unequal
longitudinal and lateral hydrodynamic dispersion. Interphase mass transfer is described
by a first-order rate expression. Solutions are presented also for the case of equilibrium
distribution of solute between fluid and solid phases. Three types of release from a
point source were considered: instantaneous release of a finite mass of solute, continuous
release at an exponentially decaying rate, and release for a finite period of time. Com-
putational results for point-source solutions show the expected variation of sorptive
retardation effects progressing from the case of no sorption, through cases of non-
equilibrium sorption, to the case of equilibrium sorption. The point-source solutions
can be integrated over finite regions of space to provide analytical solutions for regions
of solute release having finite spatial extents and various geometrical shapes, thus con-
siderably extending the utility of the point-source solutions.

1. INTRODUCTION

The s t u d y o f t r a n s p o r t o f c h e m i c a l l y reactive solutes b y f l o w i n g g r o u n d -

w a t e r s y s t e m s has m a n y a p p l i c a t i o n s t o c u r r e n t investigations in t h e fields
o f h y d r o l o g y a n d g e o c h e m i s t r y . Processes o f mass t r a n s p o r t a n d i n t e r p h a s e
mass transfer p l a y i m p o r t a n t roles in n a t u r a l systems such as ore deposits
a n d g e o t h e r m a l reservoirs. D i s t u r b a n c e s o f n a t u r a l s y s t e m s b y h u m a n activi-
ties also m a y require e v a l u a t i o n a n d p r e d i c t i o n o f rates and e x t e n t s o f mass
t r a n s p o r t . These d i s t u r b a n c e s i n c l u d e s u b s u r f a c e disposal o f radioactive
o r t o x i c c h e m i c a l wastes, acidic drainage f r o m mines, a n d leaching o f land-
fills, tailings dams, a n d spoil heaps.
T h e w o r k r e p o r t e d here is a p a r t o f a larger s t u d y o f n o n e q u i l i b r i u m
228

processes in mass transport by flowing groundwater. This work presents

analytical solutions for convective--dispersive transport of a radioactive
solute which undergoes time-dependent sorption on surfaces of the matrix
supporting the flow. The rate of sorption is represented by a first-order
kinetic rate law, corresponding to the approximation of very low sorbate
activity in the fluid phase. These solutions were derived to serve as references
for comparison with numerical results for transport problems using second-
order kinetic rate laws of sorption and with more complex treatments
including effects of thermodynamic coupling of transport processes; these
investigations are n o w in progress. For further comparison, solutions for
the case of equilibrium sorption have been included; some of these solutions
have been published before by other workers.
Studies of mass transport in one or two dimensions with a first-order
rate of nonequilibrium, interphase mass transfer have been reported by
Hougen and Marshall (1947) and Thomas (1949), who omitted effects
of hydrodynamic dispersion, and by Lapidus and Amundson (1952), Lynch
(1964), Ogata {1964, 1970), Eldor and Dagan {1972), Lindstrom and
Narasimhan (1973), Marifio (1974, 1978), Lindstrom (1976), Van
Genuchten and Wierenga (1976a, b), Cameron and Klute (1977) and Pickens
et al. {1979), who included dispersion.
The solutions presented here are geometrically symmetric a b o u t an
axis parallel to the direction of fluid flow, and include different values
of the coefficients of hydrodynamic dispersion in longitudinal and transverse
directions. The medium supporting fluid flow is assumed homogeneous and
infinite in extent. Three conditions governing release of solute are con-
sidered: ( 1 ) a n instantaneous release of a finite quantity of solute; {2)a
continuous time-dependent release; and ( 3 ) a time-dependent release which
is terminated at a finite time.
Our approach has been to derive analytical solutions to the problem of
release of solute at a hypothetical single point in space. The analytical
solutions to this problem are useful in two ways: ( 1 ) t h e point-source
solutions by themselves are useful approximations to solute concentration
histories at distances sufficiently far from source regions that the dimensions
of the latter can be considered relatively negligible; and (2) the point-source
solutions can be used as the kernels of integrals over finite volumes of
space to provide analytical solutions for source regions having finite spatial
extents and a variety of geometrical shapes. This extension allows evaluation
of solute concentration histories at source-to-observer distances which are
not large relative to source dimensions.
The solutions presented here for the cases of nonequilibrium sorption
are expressed in closed form as definite integrals in which time is the variable
of integration. These integrals appear to be irreducible, and must be
evaluated numerically. We have c o m p o s e d a c o m p u t e r code, available upon
request, which numerically evaluates the point-source solutions presented
here. See the Notation for symbols used in this paper.
 229

NOTATION
List of symbols used

B retardation factor [ dimensionless ]

C c o n c e n t r a t i o n of solute in fluid phase [M L -3 ]
Laplace transform (image) of C [M L -3 T]
Cc c o n c e n t r a t i o n , C, f r o m c o n t i n u o u s release for t < T [M L -3 ]
Cp c o r r e c t i o n to c o n c e n t r a t i o n , C, for t > T [M L-3 ]
CT total c o n c e n t r a t i o n in fluid phase of exchanging solutes [M L-3]
D second-rank tensor c o e f f i c i e n t o f h y d r o d y n a m i c dispersion [L 2 T - ' ]
DL c o e f f i c i e n t of longitudinal dispersion [L2 T-' ]
DT coefficient of transverse dispersion [L2 T-I ]
f c o n s t a n t defined below eq. 23 [dimensionless]
g f u n c t i o n of s defined below eq. A-6 [dimensionless]
h f u n c t i o n of s defined below eq. 23 [T -1 ]
I n (x) m o d i f i e d Bessel f u n c t i o n of the first kind of order n with
argument x [ dimensionless ]
Y, solute flux per unit area o f fluid phase [M L -2 T - 1 ]
J(x,y) f u n c t i o n defined in A p p e n d i x B [ dimensionless ]
kl forward rate c o n s t a n t for linear s o r p t i o n reaction IT-1 ]
k~ backward rate c o n s t a n t for linear s o r p t i o n reaction [T-' ]
k'x forward rate c o n s t a n t for ion e x c h a n g e reaction [M -1 L 3 T - 1 ]
k~ backward rate c o n s t a n t for ion exchange reaction [M -1 L 3 T - 1 ]
forward rate c o n s t a n t for L a n g m u i r s o r p t i o n reaction [M -1 L 3 T - 1 ]
backward rate c o n s t a n t for Langmuir s o r p t i o n reaction [T-' ]
Y Laplace t r a n s f o r m a t i o n o p e r a t o r IT]
.~-1 Laplace inversion o p e r a t o r IT-' ]
mo rate o f release of solute f r o m p o i n t source at zero t i m e [MT-']
ttt
mo rate o f release o f solute f r o m differential e l e m e n t o f [M L-3 T-' ]
v o l u m e source at zero t i m e
M total mass o f solute in all space at t i m e t [M]
Laplace t r a n s f o r m (image) of M [MT]
Mo mass o f solute released f r o m p o i n t source [M]
mass of solute released f r o m differential e l e m e n t o f
line source [ML-']
M~' mass o f solute released f r o m differential e l e m e n t o f
plane source [ M L -2 ]
M~" mass of solute released f r o m differential e l e m e n t of
v o l u m e source [ M L -3 ]
f u n c t i o n o f s defined b y.eq. A-5 [T :1 ]
P
Q c o n c e n t r a t i o n o f solute in solid phase [ M L -3 ]
Laplace t r a n s f o r m (image) of Q [M L -3 W]
Qsat sorptive capacity o f solid phase [ M L -3 ]
S Laplace t r a n s f o r m variable [T-I ]3 I
S rate o f transfer o f solute f r o m fluid phase to solid phase [ML- T- ]
T t i m e o f cessation of release o f solute [T]
U
___>
unit step f u n c t i o n defined b e l o w eq. 46 [dimensionless]
v fluid velocity v e c t o r [L T-' ]
v average velocity o f fluid [L T-' ]
V elemental volume of porous medium [L 3 ]
rate o f solid v o l u m e to fluid v o l u m e [ dimensionless ]
constants used in A p p e n d i x B, i ----1, 2, 3, 4 [T-' ]
V t i m e c o n s t a n t for decay o f release rate [T-' ]
c porosity [ dimensionless ]
r e d u c e d c o o r d i n a t e defined b e l o w eq. 26 [T '/2 ]
X t i m e c o n s t a n t for radioactive decay o f solute IT-' ]
230

2. THE EQUATIONS OF TRANSPORT AND INTERPHASE TRANSFER

Let us consider an arbitrary volume V of a m edi um having porosity e

and saturated by a fluid phase containing a solute species which may
undergo sorption on surfaces of the solid phase. The volume V is fixed with
respect to the external c o o r d i n a t e axes. The fluid flows with constant
pore-water velocity ~. The mass concent rat i ons of solute within V are
C mass units per unit vol um e of fluid and Q mass units per unit volume of
solid. Because the system u n d e r consideration is n o t at equilibrium, the con-
centrations C and Q are n o t constants, but are functions of position and time.
We assume th at a solute mass flux exists only in the fluid phase, i.e. sorbed
solute remains fixed with respect to the solid phase, and define a solute mass
flux in the fluid phase J~ referred to a unit area of the fluid phase. To
a c c o u n t for changes of solute mass arising from internal processes within
volume V, we h y p o t h e s i z e t ha t solute mass m ay be removed from both
fluid and solid phases by radioactive decay with a decay constant k, and
we acco u n t for interphase mass transfer by hypothesizing a mass transfer
rate S expressed as mass units of solute per unit time and volume of the
solid phase where positive S corresponds to a transfer of solute mass from
the fluid phase t o the solid phase. We t h e r e f o r e obtain the conservation
equations:
e ( a C / a t ) = - - e V " Y~ - - e k e - - ( 1 - - e ) S (1)
(1-e)'SQ/St = --(1--e)kQ + (1--e)S (2)
The flux o f solute is the mass of solute flowing per unit area of fluid phase
in unit time, and is equal to the sum of a diffusive flux and an advective
flux given by:
j, : -D. C + (3)
In deriving eq. 3 we have assumed that V" ~ is zero. The second-rank tensor
D is the coefficient of hydrodynamic dispersion and is a function of the
velocity of flow ~ (Scheidegger, 1961; Bachmat and Bear, 1964). With
this relation eq. 1 becomes:
e(~C/~t) = eV'(D'VC) --e~'VC--ekC--(1--e)S (4)
The interphase mass transfer rate S m ay assume m a n y forms. For
example, the rate expression for ion exchange in which the ionic solute of
interest replaces a n o t h e r ion o f equal charge on the solid phase is:
S = k~ ( e s , t - - Q ) C - - k ~ (CT -- C)Q (5)
where Qsat is the capacity o f the solid phase for sorption of the solute;
CT is th e total c o n c e n t r a t i o n in the fluid phase of the exchanging solutes;
and h~ and hl are f or w a r d and backward rate constants, respectively
(Hiester and Vermeulen, 1952). For a n o t h e r example, the rate expression
for Langmuir adsorption at a surface is:
 231

tt ft
S : kl(Qsa t - - Q ) C - - k 2 Q (6)
tt II
where kl and k 2 are rate constants and the other symbols have the same
meanings as before.
Eqs. 5 and 6 are both nonlinear; they may be linearized by assuming in
both that Q ~ Qsat and in eq. 5 t h a t C ' ~ Cw. Then the first-order non-
equilibrium form of S in both cases is:
S = klC--k2Q (7)
P t ?t
in which kl -~klQsat and k2 = k2CT for ion exchange, and kl - - k l Q s a t
and k2 = k~' for Langmuir adsorption. S given by eq. 7 will be used in
eqs. 1 and 2 for analysis of mass transport with first-order nonequilibrium
interphase mass transfer.
If it is assumed t h a t the fluid and solid phases are in a state of chemical
equilibrium with respect to transfer of the solute of interest, the net mass
transfer rate S is identically zero, and we proceed in the following manner.
We add eqs. 2 and 4 to obtain a mass conservation equation with respect
to a unit volume of porous medium:
e(~C/~t) + ( 1 - - e ) ' a Q / ~ t = eV'(D'VC)--eF'VC--eXC--(1--e)XQ
(8)
If our assumptions made about linearity in the nonequilibrium case can be
carried over to the equilibrium case, then we may set S equal to zero in
eq. 7 and obtain:
Q/C = k 1/k2
which provides the required relationship between Q and C.

3. SOLUTIONS OF THE EQUATIONS OF TRANSPORT

We wish to derive analytical solutions of the transport equations for

three cases which cover the entire range of sorptive behavior that can be
described by linear equations: no sorption, linear nonequilibrium sorption
and linear equilibrium sorption. We proceed by making the following
assumptions.
(1) We are working with a homogeneous porous medium of infinite extent.
(2) The fluid flow field is steady in time and uniform t h r o u g h o u t space;
fluid flows with velocity v parallel to the z-axis of a Cartesian coordinate
system in the direction of increasing z.
(3) The principal axes of the dispersion tensor are oriented parallel to the
coordinate axes; the longitudinal dispersion coefficient is D L in a direction
parallel to the z-axis and the lateral (or transverse) dispersion coefficient is
D w in any direction perpendicular to the z-axis; DL and D w a r e functions
only of the flow velocity.
232

With these assumptions, the transport equation w i t h o u t sorption is:

~C/~t = D w (~2C/ax2 + ~2C/(}y2) + D L (~2C/~z2) --v(~C/~}z) - - X C (9)
For the case of linear equilibrium sorption we have:
~C/~t = (DT/B)(~2C/Dx 2 + ~2C/~y2) + (DL/B)(~2C/~z 2)
-- (v/B)(~C/~z) -- XC (10)
Q = (kl/k2)C (11)
where B is the retardation factor defined by:
B = 1 + c~(k 1/k2) (12)
and ~ is defined by:
a = (I -- e)/e
The case of linear nonequilibrium sorption involves two simultaneous
equations:
~C/~t = D w(~2C/ax2 + a2C/~y 2 ) + D L ( ~ 2 C / ~ z 2 ) - v ( a C / ~ z ) - X C
--~(klC--k2Q) (13)
~Q/~t = - - h Q + k i C - - k 2Q (14)
Eqs. 13 and 14 should be compared to eqs. 1 and 2 of Lindstrom (1976).
We note t h a t if eqs. 13 and 14 are multiplied by e and (1 -- e), respectively,
and then added, the result is the mass balance for a unit volume of porous
medium, as expressed by our eq. 8. Lindstrom's (1976) equations 1 and 2
do n o t provide the correct mass balance.
We require solutions to eqs. 9--11 and eqs. 13 and 14 subject to the
initial conditions:
C = 0; Q = 0 for p > 0; t = 0 (15)
where p2 = x 2 + y2 + z 2 ' and the b o u n d a r y condition,

p--~
lim C = 0, t > 0 (16)

Conditions (15) and (16) will determine the required solutions up to a

multiplicative constant which will be fixed by the nature of the solute
release.
The Laplace transform with respect to time of eq. 10, the case of equilib-
rium sorption, is:
(DT/B) (a a C/~x 2 + a: C/~y 2 ) + (DL/B) (a 2 C/az 2 ) _ (v/B) (~C/az)
- (s + ~ ) ~ = 0 (17)
where the overbar indicates the transformed function (or image function)
and s is the parameter of the transformation. We note that the transform of
 233

eq. 9, the case of no sorption, is given by eq. 17 with B --- 1. The Laplace
transforms of eqs. 13 and 14 are:
DT(02~/OX2 + ~2~/~y2) + ~2~/~Z2 --v(oe/Oz)--(s +~)C
--~(kl~--k2~) = 0 (18)
sQ --- - k Q + klC--k2Q (19)
The initial conditions (15) were used in deriving eqs. 17--19. The trans-
formed boundary condition is:
lim C = 0 (20)

Solving eq. 19 for Q gives:

= k~C/(s + k + k2) (21)
Inserting eq. 21 into eq. 18 and combining terms, we obtain the following
equation for the case of nonequilibrium sorption:
DT (~2~/~X2 jr. ~2~/~y2) + D L (~2~/~z2) --v(~C/~z)
--[s+k+c~kl --c~klks/(s+k+ks)]C : 0 (22)
We now note that both eqs. 17 and 22 m a y be expressed in the general form:
(Dw/f) (OSC/Ox s + 0s C/0y s ) + (DL/f) (0SC/0z 2 ) -- (v/f) (OC/~z)
--[s+k+h(s)]C = 0 (23)
where f = 1 for the cases of no sorption and nonequilibrium sorption; and
f = B for the case of equilibrium sorption, and:
h (s) = 0 for the cases of no sorption and equilibrium sorption
h (s) = ~k 1 -- c~k 1 k2/(s + k + ks ) for the case of nonequilibrium
sorption
In order to find a complete solution of eq. 23, we need another condition
in addition to the b o u n d a r y condition (20). The second condition is a
statement of conservation of solute mass in all space and will provide a
relationship between solute concentration and the strength of a point
source releasing solute. We require t h a t the a m o u n t of solute present in all
space at any time t be equal to the total a m o u n t of solute released at the
source with correction for conversion of solute to another material by
chemical reaction or radioactive decay. Hence, if M(t) is the total mass of
solute present at t, it follows that:

f [eC + (1 - - e ) Q ] d Y M(t) (24)

all space
The Laplace transform of eq. 24 is:
234

f
all s p a c e
[eC + ( 1 - - e ) Q ] d V = M(s) (25)

The forms of the function M ( t ) and of its Laplace t r a n s f o r m / ~ ( s ) will be

determined by the temporal behavior of the solute-emitting source. Leaving
this specification open for the time being, we proceed to the solution of
eq. 23, subject to conditions (20) and (25), and find that:
= [(s + ~.)I~(S)/4?re~TDTDL 1/2 ] exp ( v z / 2 D L)
x exp [-- ~?(f(s + k + h) + v 2 / 4 D L } 1/2 ] (26)
where
?7 ---- ( r 2 / D w ~ z 2 / D L ) I / 2 ; r 2 = x 2 ..~y2

f and h remain as defined following eq. 23. A detailed derivation of eq. 26

is given in Appendix A.
Before the solution (26) can be inverted from s- to t-space, /~(s) must
be specified. In the following sections we consider several release scenarios:
(1) an instantaneous release; ( 2 ) a continuous time-dependent release; and
(3) a time-dependent release for a finite time period followed by no further
release (a "time-dependent pulse").

3.1. Instantaneous release

A quantity M 0 of solute is released instantaneously at t = 0 at the origin

of coordinates. Allowing for disappearance of solute by radioactive decay,
the quantity M ( t ) of solute present at time t is:
M ( t ) = Mo e x p ( - - k t )
The Laplace transform of M ( t ) is:
M(s) = Mo/(S + X) (27)
Inserting eq. 27 into eq. 26 gives:
= (M o/4~reT?DTDL 1/: ) e x p ( v z / 2 D L ) exp [-- 77{f(s + k + h) + v 2/4DL }1/2 ]
(28)
We n o w use eq. 28 to find C and Q for specific cases of sorptive behavior.

3.1.1. Equilibrium sorption. In this case, h(s) = 0 and f = B; the inverse of

eq. 28 is then found from tables [e.g., Erd~lyi, 1954, p. 245, equation
5.6(1)] to be:
C = [B1/2Mo exp (-- ~ t ) / 8 e D w ( ~ 3 t 3 D L ) l / 2 ]
× exp [-- Br 2/4DT t -- B (z -- vt/B) 2/4DL t] {29)
 235

and Q is then:
O = (kl/k2)C
(11)

3.1.1. Nonequilibrium sorption. Substituting f = 1 and the appropriate

value of h (s) into eq. 28 gives:
= (Mo/4ne~TDTDL v2 ) exp (vz/2DL)
×exp[--~7{s+X+v2/4DL +c~kl - - o ~ k l k 2 / ( s + X + k 2 ) } 1/2] (30)

Then, using eq. 21, we have:

= (klMo/4~e~TDTDL 1/2) exp (vz/2DL)(s + X + k2) -1
× exp [ - - ~ 7 { s + X + v 2 / 4 D L +o~kl - - O ~ k l k 2 / ( s + k + k 2 ) } 1/2 ] (31)
in eq. 30 is inverted using eq. B-13, Appendix B, with:
fll = k + V 2 / 4 D L + a k l ; [32 = a k l k 2 ; and f13 = k + k 2
The result is:

C = [Mo exp (-- Xt)/8eDT (gaDL)l/2 ] (t-3/2 exp [ - r 2 /4DT t

-- (Z - - v t ) 2 / 4 D L t - ~ k 1 t] + ( a k l k 2 ) l / 2 exp ( - - k 2 t )
t

× f e x p [-- r2 /4DT • -- (z --VT)2 /4DL T -- (O~kl --k2 )T]

o )
x I1 [ 2 { a k l k 2 r ( t - - r ) } 1/2 ] r - l ( t - r ) - l / 2 d r (32)

If we make the substitution u = r/t the second term within the large round
braces in eq. 32 becomes:
1

(akl k~ /t) In exp ( - ks t) f exp [-- r 2/4DT tU -- (z -- vtu) 2/4DL tu

0

- - (O~k 1 - - k 2 )tu] 11 [ 2 t { a k l k2u(1 -- u)} 1/2 ] U - 1 (1 -- U)1/2 du

a form useful for numerical evaluation.

In Appendix B, the inverse of eq. 31 is found to be:
t

Q = [kl M0 exp {-- (X + k2 )t}/8eDz (~'aDL)1/2 ] J exp [-- r 2 / 4 D z r

0

-- (z -- vr) 2/4DL r -- (~kl -- k2 )r] I0 [2 {txkl k2 r ( t - - r)} i n ] r - a n d r

(33)
236

or

Q = [ k l M o exp {-- (~ + k2 )t}/8eDT ('g3tDL) 1/2 ]

1

× j exp [ - - r 2 / 4 D wtu -- (z - - v t u ) 2 / 4 D L t u -- ( a k 1 - - k 2 ) t u ]
o

× Io[2t{aklk2U(1 - - u ) } 1/2 ] u - 3 / 2 d u

3.2. C o n t i n u o u s t i m e - d e p e n d e n t release

Solute is released continuously at the origin beginning at t = 0. The rate

of release is m0 mass units per unit time at t = 0, and decreases exponen-
tially with time with a time constant 7 independently of radioactive decay;
simultaneously, solute disappears from the source and from the transport
system by radioactive decay with a decay constant k. Then at time t the net
rate of change of solute mass M ( t ) in space is:
dM(t)/dt = m o exp [-- (7 + k)t] -- k M ( t ) (34)
with the initial condition,
M(0) = 0 (35)
The Laplace transform of M ( t ) obtained from transforming eq. 34 and
substituting eq. 35 is:
.~(s) = m o / [ ( s + ~)(s + ~. + 7)] (36)
Inserting eq. 36 into eq. 26 gives:
= (m o/4~e~?DTDL 1/2 ) exp ( v z / 2 D L )(s + k + 7)-1
× exp [-- ~?{f(s + ~ + h) + v 2 / 4 D L } 1/2 ] (37)

3.2.1. E q u i l i b r i u m sorption. With h (s) = 0 and f = B, eq. 37 becomes:

= (mo/4~e~?DTDL 1/2 ) exp ( v z / 2 D L ) ( S + ~ + ~,)-1
× exp [-- ~?{B(s + ~) + v 2 / 4 D L } 1/2 ] (38)
In Appendix B, the inverse of eq. 38 is found to be:
C = Ira0 exp {-- (7 + h)t}/87reT?DTDL 1/2 ] exp ( v z / 2 D L )
× [exp {-- ~?(v 2/4DL -- 9[B) 1/2 } erfc {½77( B / t ) 1/2 -- (v 2 t / 4 D L B -- ~,t) 1/2 }
+ exp {+ ~7(v2/4DL --~,B) 1/2 }
× erfc {½~?( B / t ) 1/2 + (v 2 t / 4 D L B -- ~[t) 1/2 }] (39)
If v 2 / 4 D L -- ~, ~ O, the following result can be derived from eq. 39 using
an infinite-series approximation for the error function with complex argu-
ment (Gautschi, 1964, p. 299, equation 7.1.29):
 237

C ~ [m0 e x p { - - ( 7 + k)t}/47re~?Dw DL '/2 ] e x p (vz/2DL)

× (erfc{½~?(B/t) 1/2 } cos {~(TB -- v:/4DL) in }

+ (~7)-*(t/B) in e x p (--BT?2/4t)[1 -- cos {~?(TB -- v2/4DL)V2}]

+ 2~Tr-l(B/t) 1/2 e x p (--B~72/4t) ~ [ e x p (--¼m2)/(m 2 + B~72t-')]

m=l
\

× [cosh {m(7 -- v2/4DL B) in } -- cos {~?(TB -- v2/4DL)V2}])

If V2/4DL B ----7 =/= 0, t h e n eq. 39 b e c o m e s :

C = [m0 e x p { - - ( 7 + k)t}/4~eT?Dw DL *n] e x p (vz/2Dn) erfc [½~?(B/t) in]
N o t e t h a t b o t h C and Q are u n b o u n d e d at 77 = 0.

3.2.2. Nonequilibrium sorption. In this case eq. 37 becomes:

= (mo/4~e~?DTDL v2) e x p (vz/2DL)(S + ~ + 7 ) -1
× e x p i--~7{s + k +v2/4DL + O~kl --oLklk2/(s + k + k2)} 1/2 ] (40)
and eq. 21 b e c o m e s :
= (klmo/4~e~?DTDL 1/2) e x p (vz/2DL)[(s + k + 7 ) ( s + k + k2)] -1
x e x p [--~7{s + k + v2/4DL + a k l --O~klk2/(s + k + k2)} 1/2 ] (41)
In A p p e n d i x B, the inverse o f eq. 40 is d e t e r m i n e d t o be:

C = [too e x p [-- (7 + k)t]/8eDT(Tr3DL)W2] i

t
x f exp [--r 2 / 4 D T r -- (z -- V~')2/4DLT + 7T{'I+ akl/(k2 --7)}]
0
x J[c~k 1k2T/(k2 -- 7),(k2 -- 7) (t - - r ) ] r -3/2 d r (42)
T h e f o l l o w i n g f o r m o f eq. 42 is c o n v e n i e n t f o r n u m e r i c a l evaluations:
C = [m0 e x p { - - ( 7 + k)t}/8eDT(lr3tDb) in]
1

X e x p [-- r2/4DTtU -- (z -- vtu):/4DL tU + 7tu {1 + a k l / ( k 2 -- 7)}]

0

x J[c~k 1k 2 tu/(k 2 -- 7 ) , t ( k 2 -- 7 ) ( 1 -- u)] u -an du

In a p p e n d i x B, t h e inverse o f eq. 41 is f o u n d t o be:

Q = [kl/(k:--7)] (C--moexp{--(k+k2)t}/8eDT(Tr3DL) 1/2

\
t
x~ e x p [ - - r 2 / 4 D T ' r -- (z --Vr)2/4DLT -- ( ~ k l - - k : ) T ]
0
238

x Io[2{aklk2r(t--r)} v2]r -an dr) (43)

where C is given by eq. 42. After the change of variables r = t u , eq. 43

becomes: /

Q = [ k l / ( k 2 --3`)] ( C - - m o e x p { - - ( k + k 2 ) t } / 8 e D w ( T r 3 t D L ) 1/2
\
I

× exp [-- r 2 / 4 D T t u - - ( z - - v t u ) 2 / 4 D L t u - - ( ~ k 1 - - k2 ) t u ]
o )
x I o [2t{o~klk2u(1-- u)}V2]u - a n du

If 3' = O, which corresponds to a rate of solute release affected only by

radioactive decay, eq. 43 becomes:
Q = k~ k~ 1 [m0 exp (--Xt)/8eDT(TrSDL)~nl
t

x f exp [-- r 2 / 4 D T r - ( z - - v r ) 2 / 4 D L r l {1 - - J [ k 2 ( t - - r ) , a k l r] }r -a/2 dr

0 (44)
in which eq. B-8, Appendix B, has been used.
If 3" = k: :~ 0, the following expressions are obtained for C and Q:
C = [m o exp {-- (~ + k 2 ) t } / 8 e D T ( l r a D L ) 1/2]
t
× I exp [-- r : / 4 D T r - - (z - - v r ) : / 4 D L r - - ( a k l - - k 2 ) r ]
o

× I0 [2 {akl k2 r ( t - - r ) } 1/: ] r - a n dr
Q = [hi mo exp {-- (k + k 2 ) t } / S e D w ( ~ a D L ) 1/:]
t

x dr ~- exp [-- r 2 / 4 n T u - - (z - - V U ) : / 4 D L U - - ( a k 1 - - kE)U]

o o

x I 0 [ 2 { a k l k 2u(1 -- u)} v 2 ] u - a / : d u
Note that both C and Q are u n b o u n d e d positively at ~ = 0.

3.3. T i m e - d e p e n d e n t p u l s e release

Solute is released at the origin beginning at t = 0. The rate of release is m0

mass units per unit time at t = 0, and decreases exponentially with time with
a time constant 3` independently of radioactive decay; simultaneously, solute
disappears from the source and from the transport system by radioactive
decay with a decay constant ~. The release proceeds from t = 0 until t = T,
when it stops; transport of previously released solute continues after time T.
At any time t the net rate of change of solute mass M ( t ) in all space is:
 239

d M ( t ) / d t = mo exp [-- (7 + ),)tl [U(t) -- U(t -- T)] - - h M ( t ) (45)

with the initial condition:
M(0) = 0 (46)
U(t) is the unit step function, defined by:

= [0, for t~<0

U(t)
1, for t ~0

We form the Laplaee transform of eq. 45, use eq. 46 and solve for ~7(s):
ffI(s) = [mo/(S + k)(s + k + 7 ) l [ 1 - - e x p { - - T ( s + k +7)}] (47)
Inserting eq. 47 into eq. 26 gives:
= (mo/47re~DTDL 1/2) exp (vz/2DL)(S + )~ + 7) -1
× exp[--~?{f(s+~+h)+v2/4DL}l/2][1--exp{--T(s+~+7)}] (48)
It is evident that at any time t less than or equal to the "shut-off t i m e " T
concentrations in the fluid and solid phases are given by the appropriate
expressions for a continuous time-dependent release. For a time t greater
than T, the concentration in either phase is composed of the difference of
two terms, one term being the hypothetical concentration that would be
c o m p u t e d for a continuous release up to time t and the other term being a
correction to account for the cessation of solute release at time T.

3.3.1. Equilibrium sorption. The fluid concentration at time t, t > T, is:

C = Cc -- Cp
where Cc is given by eq. 39 and Cp is given by:
Cp(t) ~ exp [-- (7 + k ) T ] C c ( t -- T )
Then the concentration in the solid phase is:
Q = (kl/k2)C
At a time t, t ) T, Cp cannot be evaluated at the point r = z = 0 (7 = 0)
because I? appears in the denominator of eq. 39. In this case, C is evaluated
by direct integration of a modified version of eq. B-14 in Appendix B:

C -- [m 0B 1/2 exp {--(7 + ~)t}/8eDT(Tr3DL) 1/2]

t

X exp [r(7 -- v 2 / 4 D L B ) ] r -3/2 dT

t-T
= m o B1/2 exp [-- (7 + k)t]/4eDT(Tr3DL) 1/2 [(t -- T ) -1/2
x exp {(t -- T)(7 -- v2/4DLB)} -- t -1/2 exp {t(7 -- v2/4DLB)}
240

+ 7fl/2(v2/4DLB - - 7 ) 1/2 err {(t -- T)I/2(v2/4DLB - - ")t) 1/2 }

- - 7]"1 / 2 ( v 2 / 4 D L B -- 7) 1/2 erf { t v2 (v 2/4DLB -- 7) 1/2}] (49)

If v 2 / 4 D L B - - 7 < O, the following result can be derived using the infinite
series approximation for the error function with complex argument given by
Gautschi (1964, p. 299, equation 7.1.29):
C = [mo BI/2 exp {--(~, + X)t}/4eDT(~r3DL) 1/2 ]
I

x ( t -- T) -1/2 exp {(t -- T)(7 -- v2/4DLB)} -- t -1/2 exp{t(7 --v2/4DLB)}

+ 7r-1/2 (3' -- V2/4DL B) [t v: -- (t -- T) 1/2 ]

+ 27r-1/2(7 --v2/4DLB)Iar ~ exp(-- ¼m2) rn -1 sinh [m{t(7 --v2/4DLB)} v2 ]

rn--0

- - 2~'-1/2(7-- v2/4DLB) 1/2 ~- exp (-- ¼m2)m -1

rn=0

x sinh [m{(t -- T)(7 -- v2/4DLB)} v2 ] ) (50)

3.3.2. Nonequilibrium sorption. The fluid concentration at time t, t > T, is:
c = co-cp
where C¢ is given by eq. 42 and Cp is given by:
Cp(t) = exp [-- (7 + k ) T ] C ¢ ( t - T)
The solid phase concentration at time t, t > T, is:

Q = Qc - Qp
where Q¢ is given by eq. 43 and Qp is given by:
Qp(t) = e x p [ - - ( k + k 2 ) T ] Q ¢ ( t - - T )
If 7 = 0, Qc is given by eq. 44 and Qp is given by:
Qp = k I k21 [m 0 exp ( - - ~ t ) / 8 e D x ( l r 3 D L ) 1/2]
t-T

x exp [-- r2/4Dw r -- (z -- VT)2/4DL r]

o
x [1 - - J { k 2 ( t - - T - - r ) , ~ k l r } ] r -3n d r (51)

4. C O M P U T A T I O N A L RESULTS

Calculations were made for the solutions given in the previous section
corresponding to each type of solute release and sorptive behavior. The
 241

integrals were evaluated numerically using Simpson's form ul a (Dahlquist

and Bj6rck, 1974, p.267). Values f o u n d in the literature on mass trans-
p o r t through porous media (e.g., B r e d e h o e f t and Pinder, 1973) were used
as a guide for the choice of the following parameter values used in the
calculations:
D L = 7 m 2 yr. -1 ; DT = 2 m 2 yr. -1
v = lmyr.-l; e = 0.2; ~ = 0
The source decay cons t a nt 7 was n o t included in the c o m p u t e r program, so
the calculations cor r es pond to solutions for 7 = 0.
Fig. 1 shows the results of cont our i ng the c o n c e n t r a t i o n data at a c o n t o u r
level o f 1 0 - ' ° M in the fluid phase. Results for the cases of no sorption,
equilibrium sorption and nonequilibrium sorption, the latter with varying
rate constants, have been superimposed in each subfigure to com pare the
effects o f different types of sorptive behavior. Fig. 1A shows c o n c e n t r a t i o n
isopleths for the three types of sorptive behavior 10 yr. after an instantaneous
release of one mole of solute at r = 0, z = 0. Fig. 1B shows the resulting
isopleths after 10 yr. of c o n t i n u o u s solute release at r = 0, z = 0 at the rate
o f I mol yr. -I, and Fig. 1C shows the isopleths 9 yr. after the cessation of a
1-yr. period o f solute release at r = 0, z = 0 at the rate of 1 mol yr. -1 .
It is clear f r o m the figures t hat the isopleths for nonequilibrium sorption
for varying rate constants fall between the isopleths for the cases of no
sorption and equilibrium sorption. In a nonsorbing medium, t ransport of
the solute is n o t retarded relative t o the average m o t i o n of the fluid phase.
In the presence of nonequilibrium sorption, interphase mass transfer occurs
at a rate d e t e r m i n e d by the magnitudes of t he forward and backward reac-
tion rate constants, kl and k2, as shown in eq. 7. At the leading edge of a
solute f r o n t the ratio Q/C, and thus also the ret ardat i on factor B calculated
f r o m this ratio, increase as the magnitudes of the rate constants increase
and as the residence time o f a parcel of fluid within an elemental volume of
the fluid--solid system increases. In the equilibrium state, b o t h Q/C and B
achieve their m a x i m u m values given by eqs. 11 and 12.
To show th at the nonequilibrium solution tends to the equilibrium
solution as the rate constants increase, consider the expression for the mass
transfer rate S rewritten in terms of Q, obt ai ned by rearranging eq. 7 :
Q -~- (kl/k2) C - (1/~2) S
Then as k~ and k2 increase while the ratio k~/k 2 is kept constant, 1/k2 goes
to zero and the expression f or Q approaches t h a t of the equilibrium case,
(eq. 11). The units o f kl and k2 in t he equation above and in the following
discussion are yr. -1 .
Fig. 1 shows t hat as the values of the rate constants increase while the
ratio kl/k2 is k e p t constant, the nonequilibrium solution tends to the
equilibrium solution. The calculations for the equilibrium case were made
242

Legend
No sorption
Equilibrium sorption
k~= 0,01, k2= 0,001
Non - equili bri um sorption
k I= 0,01, k2= 0,001
kl= O,I,k2 = 0,01
kl= I,k2=O,I

40
®
30
2O
I0
v
E 0 ~ • : •

I0
• , ,, ".~ . ~,,~"

./" . / , .

-%. -... . . . . .--- ~

20
30

~4o -20 () 20 40 6() 80

z(m)

40 I ,
®

2O
I0
E 0
• % ., ." • .

I0
2O
3O

4~40 -20 2() 4() 6() 80

z(m)
 243

40
©
30
20
I0
E 0

I0
20
30
40 I 1

-4o -2o 6 20 4S 80
z(m)
Fig. 1. C o m p a r i s o n o f d i f f e r e n t s o r p t i v e b e h a v i o r s h o w i n g t h e l o c a t i o n o f c o n c e n t r a t i o n
i s o p l e t h s o f 1 0 -1° m o l e s o f s o l u t e p e r l i t e r in t h e f l u i d p h a s e :
A. T e n y e a r s a f t e r o n e m o l e o f s o l u t e w a s i n s t a n t a n e o u s l y r e l e a s e d a t r ---- 0, z ---- 0.
B. A f t e r t e n y e a r s o f c o n t i n u o u s r e l e a s e o f s o l u t e a t t h e r a t e o f l m o l y r . -1. S o l u t e
r e l e a s e d a t r = 0, z --'--0.
C. N i n e y e a r s a f t e r c e s s a t i o n o f a c o n t i n u o u s r e l e a s e o f s o l u t e f o r a 1-yr. p e r i o d . S o l u t e
r e l e a s e d a t r ---- 0, z = 0 a t t h e r a t e o f I m o l y r . -1 .

f o r kl = 0.01 and ks = 0 . 0 0 1 , so k l / k 2 = 10. N o t e t h a t the rate c o n s t a n t s

k l and k2 d o n o t a p p e a r individually in t h e equilibrium s o l u t i o n , b u t o n l y in
t h e ratio k l/k2. F o r t h e n o n e q u i l i b r i u m s o r p t i o n s o l u t i o n , calculations were
m a d e f o r k I = 0.01, 0.1 a n d 1.0, w h e r e ks was d e t e r m i n e d b y t h e ratio
k l / k 2 = 10.
T h e i n f l u e n c e o f the f l o w field (v = l m y r . -1 in t h e d i r e c t i o n o f t h e posi-
tive z-axis) and o f t h e d i f f e r e n t longitudinal and lateral dispersion c o e f f i c i e n t s
( D L - - 7 m 2 y r . - l , DT = 2 m s yr. -1) can be seen in t h e l o c a t i o n and shape o f
t h e isopleths. W i t h o u t a f l o w field, t h e isopleths w o u l d be circular and cen-
t e r e d at r = 0, z = 0. T h o u g h n o t s h o w n o n t h e figures, t h e 10-2°-M isopleth
f o r t h e n o n - s o r p t i o n case w o u l d fall w i t h i n a rectangle f o r m e d b y r = 50 m
and z = + 110 m, whereas a rectangle f o r m e d b y r = 14 m, z = + 16 m w o u l d
c o n t a i n the 10-2°-M isopleth f o r t h e e q u i l i b r i u m case. In a c c o r d a n c e with
t h e discussion a b o v e , all t h e 10-S°-M isopleths f o r n o n e q u i l i b r i u m cases
w i t h varying rate c o n s t a n t s fall b e t w e e n t h o s e f o r t h e n o n - s o r p t i o n and
e q u i l i b r i u m cases.
A c o m p a r i s o n o f Fig. 1B t o Fig. 1A and t o Fig. 1C shows o n l y a slight
d i f f e r e n c e b e t w e e n sets o f isopleths. E x a m i n a t i o n o f c o n c e n t r a t i o n values
n e a r the p o i n t o f release reveals t h a t t h e c o n c e n t r a t i o n is o n e t o t w o orders
o f m a g n i t u d e higher f o r t h e c o n t i n u o u s release case t h a n f o r e i t h e r o f t h e
o t h e r release t y p e s . F o r t h e c o n t i n u o u s release case, the c o n c e n t r a t i o n n e a r
t h e p o i n t o f release, at r = 2 m , z = 0, is b e t w e e n 2 "10 -s and 7 • 10 -s M;
244

f o r the instantaneous release case, at r = 0, z = 0, the range is 2 " 10 - v -

4 " 1 0 - 6 M ; and for the 1-yr. c o n t i n u o u s release case, 10-7--5 " 1 0 - 6 M ,
also at r = 0, z = 0. Calculations for times larger than 10 yr. show more
appreciable differences between results f o r di fferent release mechanisms.

5. E X T E N S I O N O F S O L U T I O N S TO F I N I T E S O U R C E S

The point-source solutions developed in earlier sections can be used to

c o n s t r u c t solutions resulting f r o m n o n - p o i n t sources. The t erm non-poi nt
source is used to denot e one-, two- or three-dimensional regions which
contain a u n if or m distribution of poi nt sources. The c o n c e n t r a t i o n at a
p o in t outside the source region is the sum of the cont ri but i ons from each
p o i n t source in the source region. Thus, the point-source solutions must
be integrated over t he space occupied by the n o n - p o i n t source. These inte-
grations m a y be simplified by a change of coordi nat e system or by aligning
the source region with the c o o r d i n a t e axes and making use of an axis or a
plane of s y m m e t r y .
In a Cartesian coor di na t e system, one or m ore of the following integrals
will occur in almost every solution:
U 2

f exp [-- S(u -- u')2 / 4 D t ] d u ' = (TrDt/B) 1/2 [erf {B1/2(u -- u l )/2 (Dr) 1/2 }
U 1

- - e r f { B l / 2 ( u -- u 2 ) / 2 ( D t ) i / 2 } ] (52)
where u = x, y or (z -- v t / B ) ; u' = x', y' or z'; and D = D w for u = x, y or
D = DL for u = z. Multiple integrations will result in product s of error
functions. The arguments of the error functions will in most cases involve
the time variable, and t h e r e f o r e , the error functions will be part of the
integrand in the integrations with respect to time. Though the integrands
are quite complicated, there are m a n y available software routines which
c o m p u t e error functions and Bessel functions quickly and efficiently.
A p p r o x i m a t i o n o f volume sources by p o i n t sources is reasonable when the
distance b etween the source region and the poi nt of calculation is large.
A spherical source could be a p p r o x i m a t e d by a p o i n t source and a cylindrical
source by a line source. It is difficult, however, to det erm i ne the range of
validity o f such a p p r o x i m a t i o n s by means o t h e r t han direct calculations.
Examples of non-point-source solutions derived f r o m our point-source
solutions are given in this section. The case o f an instantaneous release with
equilibrium sorption is emphasized in the examples because the exponent i al
t e r m involving spatial variables which occurs in this case also occurs in all
o t h e r cases. Aside f r o m this, the selection o f examples is eclectic.

5.1. L i n e s o u r c e

Consider a line source consisting of a distribution of p o i n t sources along a

 245

line parallel to the x-axis b e t w e e n xl a n d x2, a n d intersecting t h e y--z plane

at the p o i n t ( y ' , z ' ) . Then the c o n c e n t r a t i o n at t h e p o i n t ( x , y , z ) is given by:
x2
C(x,y,z; t) I rme source = ~ C ( x - - x', y - - y ' , z -- z'; t) Ipoint source dx'
X 1

Specifically, in the case of i n s t a n t a n e o u s release with equilibrium sorption:

C = [M0 exp ( - - k t ) / 8 7 r e t ( D w D L ) 1/2]
X exp [ - - B ( y -- y ' ) 2 / 4 D T t -- B ( z - - z ' -- v t B -1 )2/4D L t]
x [erf{B1/2(x --xl)/2(Dwt) 1/2 } - - e r f { B l n ( x --x;)/2(Dwt)l/2}] (53)
where M0 is the mass release per unit length, Mo = M o / ( X 2 - - X l ) . If the
center of the line source is located at the origin of the c o o r d i n a t e system,
t h e n in eq. 53 y ' = 0, z' = 0, x 1 = - - L / 2 a n d x2 = L / 2 , where L is the length
of the line source. If the line source is infinite, then:
C = [M 0 e x p ( - - k t ) / 4 7 r e t ( D w D L ) 1/2]
x exp [ - - B ( y -- y ' )2/4DT t - - B ( z - - z' - - v t B -1 )2/4D L t] (54)
The solution for a line source along the z-axis is slightly d i f f e r e n t in form.
F o r the i n s t a n t a n e o u s release, equilibrium case,
C = [M0 e x p ( - - k t ) / 8 7 r e t D T ] exp [ - - B ( x 2 + y 2 ) / 4 D w t ]
x [erf { B 1/2 (z - - z l -- v t B - 1 ) / 2 (DL t) 1/2 }
-- erf {B 1/2 (z - - z2 -- v t B -1 )/2 (D L t)1/2 }] (55)
where the line source e x t e n d s f r o m z = Zl to z = z 2.

5.2. D i s k s o u r c e

Next consider a disk source of radius R in the x--y plane centered at

z = z'. After changing to a radial c o o r d i n a t e s y s t e m :
R 2~r

C ( r , z , O ; t)ldi.~k ,ource = f r'dr' f C ( r - - r ' , z - - z ' , O - - O ' ; t) lpoint,o,ree dO'

0 0

In the case of i n s t a n t a n e o u s release w i t h equilibrium sorption:

C = [M~' exp ( - - k t ) / 8 e D T ] (B/lraDLta) In
x exp [ - - B ( z -- z' -- v t B -l )2/4D b t - - B r 2 / 4 D T t]
R 2~

x fexp(--Br'2/4DTt)r'dr ' f exp[--(Srr'/2DT t) c o s ( 0 ' - - 0 ) ] d 0 ' (56)

0 0
where M0' is the mass i n s t a n t a n e o u s l y released per u n i t area, M o' = M o / ( 2 1 r R 2).
As long as the integration with respect to 0' is over a period o f 21r, the limits
246

of integration can be replaced by 0 and (0 + 27r). After a change of variable,

0" = 0' -- 0, the solution becomes:
C = [M 0, exp ( - - ) k t ) / 4 e D T ] (B/TrDLt3) 1/2
× exp [ - - B ( z -- z' -- vtB -1)2~4DE t -- Br2/4DT t]
R
× | exp ( - - B r ' 2 / 4 D T t ) I o ( B r r ' / 2 D T t ) r ' d r ' (57)
0

where the integral with respect to 0" is given by Watson (1966, p. 79, equa-
tion 3.7(9)). This form shows the radial s y m m e t r y of the solution, a result
expected from the geometry of the problem. Using the definition of the
function J ( x , y ) in eq. B-7, Appendix B, the final solution can be written:
C : [M 0' exp ( - - X t ) / 2 e ( B T r D L t ) 1/2]
x exp [ - - B ( z -- z' -- vt/B)2/4DL t] [1 -- J ( B R 2 / 4 D T t , B r 2 / 4 D T t ) ] (58)

5.3. Spherical source

The solution for a spherical source region with radius R, centered at the
origin of coordinates, is most easily developed by superposition of disk
sources in the x---y plane, centered on the z-axis at z = z' and with radii R'
given by R '2 = R 2 - - z '2 . Thus, in cylindrical coordinates:
R N/,R2 - z'2

C(r,z; t) [ spherical souzc e = f dz' f r' dr'

-R 0

2~

x f C(r--r', z - - z ' , 0--0'; t) lpoint source dO'

0

For the case of instantaneous release with equilibrium sorption, superposition

of disk sources gives:
R

C = M0" exp ( - - X t ) / 2 e (BrrDL t) 1/2 f exp [ - - B ( z -- z ' - - vtB -1)2/4DL t]

-R
x [1 -- J { B ( R 2 -- z ' 2 ) / 4 D T t,Br2/4DT t}] dz'

= (M~"/2Be) exp ( - - X t ) ( e f t {B 1/2 (z + R -- vtB -1 )/2(DL 01/2 }

- - err {B 1/2 (z -- R -- vtB -1)/2 (DL 01/2 }

R

- - (B/rrDL t)'/2 f exp { - - B (z -- z' -- vtB -1 )2/4DL t }

-R

x J { B (R 2 -- z '2)/4D~ t,Br2/4DT t } d z ' ) (59)

 247
?if Hf
where M0 is the mass instantaneously released per unit volume, M0 =
M0/(~ ~R 3 ).

5.4. Cylindrical sources

For a cylindrical source of length L and radius R, centered at the origin of

coordinates with axis along the z-axis:
L/2 R

C(r,O,z; t)'cylindricalsourc e = f dz' ~ r ' d r '

-L/2 0

21r

f C(r--r', 0--0', z - - z ' ; t)]point source d0'

0

The necessary integration with respect to z' is that used in the line source
example and the integrations with respect to 0' and r' are those used in the
disk source example. The final expression for the concentration for the case
of instantaneous release with equilibrium sorption involves the p r o d u c t of
those integrations:
C = (Mo"/2Be) exp ( - - k t ) [ 1 -- J ( B R 2 / 4 D T t,Br2/4Dw t)]
× [erf {B 1/2 (z + ½L -- vtB -1 )/2 (D L 01/2 }
-- erf {B v2 (z -- ½L -- vtB -l )/2(D L t)l/2}] (60)
tft
where M0" is the mass instantaneously released per unit volume, M0 =
Mo/(TrR2 L).
As another example, we state the solutions for C and Q in the case of a
continuous, time-dependent release with nonequilibrium sorption, using the
same geometry as that just considered:
t

C = (mo'/2e) exp [-- (~ + 3,) t] f [1 -- J ( R 2 / 4 D T T, r2/4Dw r)]

0

x [erf{(z + ½L -- v r ) / 2 ( D L r ) v 2 } - erf{(z -- ½L -- vr)/2(DLr)l/2}]

× exp [Tz{1 + c~kl/(k2 --7)}]J[C~klk2r/(k2 --~/),(k2 - - 7 ) ( t - - r ) ] dr (61)
Q = [ k l / ( k 2 --')')(C -- (mo'/2e) exp [--(X + k2)t]
t
X f [1 - - J ( R 2 / 4 D T r , r 2 / 4 D T r ) ] I o [ 2 { c ~ k l k 2 r ( t - - r)} 1/2]
0

x [erf {(z + ½L -- v r ) / 2 ( D L r ) 1/2 } -- erf {(z -- ½L -- v r ) / 2 ( D b r ) l n } ]

x exp [-- (~k t -- k2)z] d z ) (62)

tH ftP
where m 0 is the rate of release of mass per unit volume, m o = m o/(IrR 2 L).
248

Finally, consider a cylindrical source region having length L and radius R,

centered at the origin of coordinates, with its axis coincident with the y-axis.
Here:

C(x,y,z; t) l c y l i n d r i c a l source

-~L R +(R 2 - z'2) 1/2

: ~ dy' f d z ' f C(x--x',y--Y',Z--Z',t)[pointsourc e dx'

--1 L -R - ( R 2 - z ' 2 ) 1/2

For the case of an instantaneous release with equilibrium sorption, it follows

that:
C = [Mo" exp (--Xt)/8e (BTrDLt) 1/2]
x [erf {B 1/2 (y + ½L)/2 (D T t ) 1/2 } -- erf {B 1/2 (y -- ½L)/2 (D T 01/2 }]
R
x f exp [--B(z--z'--vtB-1)2/4DL t]
-R
x { e r f [ B 1/2 {x -{- ( R 2 - - z t2 ) 1/2 } / 2 ( D T t) 1/2 ]

- - e r f [ B 1/2 {x - - ( R 2 - - z '2) 1/2 } / 2 ( D T t)1/2 ] } d z ' (63)

6. DISCUSSION

We have derived analytical solutions to the transport equation under the

assumption that the n u m b e r of sites, on surfaces of the solid phase, available
for either ion exchange or the Langmuir t y p e of sorption is very large
relative to the n u m b e r of sites occupied by sorbate ions or molecules. This
assumption leads to a kinetic law for the rate of mass transfer between fluid
and solid phases which is first order in concentrations of sorbate in both
phases. Thus, our analysis is strictly applicable only to sorption upon a solid
phase in which the concentration of sorbate is small relative to the saturation
concentration or, equivalently, to sorptive systems characterized by a linear
isotherm for sorption.
The point-source solutions serve as standards for checking, and compari-
son with, numerical models with second-order rate laws for sorption, now
being studied. Additionally, the point- and line-source solutions axe useful
approximations, in the far field, to solutions of linear transport problems
involving source functions for which a total rate of release of sorbate can be
specified. Finally, the point-source solutions axe directly applicable to the
development of analytical solutions of problems involving source functions
occupying finite regions of the space in which transport takes place. This
application is possible because the transport equation and, in the case of
 249

nonequilibrium sorption, the associated mass transfer equation are linear

equations, and the principle of superposition can be used to c o n s t r u c t the
analytical expressions for finite sources.
It is a characteristic of point-source solutions t hat t h e y may becom e
infinite at the p oi nt where mass is i n t r o d u c e d into the t ransport system. In
our derivations, this p o i n t is the origin of the coordi nat e axes (r = 0, z = 0).
In the following paragraphs we discuss the behavior of the point-source
solutions at this poi nt for each t y p e of mass release.
Instantaneous release. In this case, the expression (29) for equilibrium
sorption is finite everywhere when t ) 0, and as t ~ 0 expression (29) tends
to zero at all points e x c e p t the origin where it becomes infinite, as expected.
F o r nonequilibrium sorption, eq. 32 for C exhibits identical behavior;
however, the integrand in this expression appears to becom e infinite for
r = z = 0 at the lower limit of integration when t ~ 0. This apparent singu-
larity can be r em oved by a change of the variable of integration from ~ to T2 ,
and by using the limiting f o r m of the modified Bessel f u n c t i o n for vanish-
ingly small values of its argument. On the ot her hand, the integrand in the
expression for Q in eq. 33 has a non-removable singularity at the lower limit
o f integration (T = 0) when r = z = 0 and t ~ 0. This behavior is a conse-
quence of our assumption that the sorptive capacity of the solid phase is
unbounded.
Continuous release. As expect ed, all solutions becom e infinite at r = z = 0
when t ) 0.
Pulse release. Here the solutions for equilibrium sorption clearly are
b o u n d e d at the poi nt r = z = 0 when t ~ T. For nonequilibrium sorption,
the integrands in the expression for C f o r m e d by subtracting the solution for
the pulse release f r om the solution for the cont i nuous release appear to
b e co me infinite at their lower limits when r = z = 0 and t ~ T, c o n t r a r y to
e x p ectatio n . It can be shown by t w o partial integrations t h a t this apparent
singularity is removable. On t he o t h e r hand, the integrands in the c o m p l e t e
expression for Q have non-removable singularities at their lower limits when
r = z -- 0 and t ) T, again because of the assumption o f infinite sorptive
capacity in the solid phase.
The singularities in Q in the cases of nonequilibrium sorption following an
instantaneous release and cessation of a pulse release are n o t significant limi-
tations to application of the point-source solutions. First, in the use of these
solutions as ap p roxi m a t i ons of solute c o n c e n t r a t i o n histories in the far field
there will be little, if any, interest in the p o i n t r = z = 0. Secondly, when the
point-source solutions are integrated in space to form solutions for spatially
finite source regions all singularities, b o t h real and apparent, disappear.
It should be n o t e d that solutions f or finite source regions, derived f r o m
our point-source solutions, describe transport away from source regions
which have physical and chemical properties identical to those of the sur-
rounding medium, e x c e p t t hat mass is i n t r o d u c e d within the source regions.
In particular, the source regions do n o t pe r t urb the fluid flow field. Thus, for
250

example, these solutions do n o t describe transport of a solute which is

introduced at the surface of a region of space which is impervious to fluid
flow.

ACKNOWLEDGMENT

This work was performed for the Director, Office of Energy Research,
Office of Basic Energy Sciences, Division of Engineering, Mathematics and
Geosciences, of the U.S. Department of Energy under contract DE-AC03-
76SF00098.

APPENDIX A -- DERIVATION OF eq. 26

We make the following changes of variables:

5 = Cexp(--vz/2DL); Xl = X(DL/DT)I/2; Yl = Y(DL/DT) 1/2
Then eq. 23 becomes:
02-U/~X 21 + ~2~/~y2 + ~2~l/~Z2 __ f D L - l ( s + )k + v 2 / 4 D b f +h)~t = 0 (A-l)

and the boundary condition (20) becomes:

lim ~ = 0, where p~ = x ~ + y ~ + z 2 (A-2)
,O1 - - ~ o o

Eq. A-1 is spherically symmetric in the coordinate system with axes x 1, Y1, z;
therefore eq. A-1 can be recast in the form:
d 2 u / d p l2 + 2 p l 1 "du/dPl -- f D L - l ( s + k + v2/4DLf + h)u = 0 (A-3)
where Pl is the radial coordinate defined in (A-2). The general solution of
eq. A-3 consistent with (A-2) is:
= ( A / P l ) e x p [ - - p l (fDT.-I)'/2(s + k + v 2 / 4 D b f + h) 1/2]

where A is a constant of integration. Then C is given by:

= (A/77DL 1/2) exp [VZ/2DL --~7(fp) 1/2 ] (A-4)
where ~ was defined following eq. 26, and:
p = s + ~ + v2/4DLf + h (A-5)
We next evaluate A using the mass balance expressed by eq. 25 and noting
t h a t Q can be related to C b y :
= gC (A-6)
where g is a function of the transformation parameter s and is given by:
 251

g(s) = k,/(s + k + k2), for the case of nonequilibrium sorption

g(s) = k~/k2, for the case of equilibrium sorption
g(s) = O, for the case of no sorption
We substitute eqs. A-4 and A-6 into eq. 25 and use the volume element
dV = 27rr dr dz; the result is:

(2~re/Dl)/~)(1 + ~g)A ; exp (vz/2DL) dz

--o0

e x p [-- (fp)l/2 (r2/DT + z2/DL)I/2] ~- /~(S)

× rdr (r2/DT + z2/DL)I/2 (A-7)
o
To integrate eq. A-7, let r? = (r2/DT +z2/DL ) i n ; then eq. A-7 becomes:

(27re/DLV2)DT(1 + ag)A ; exp (vz/2DL)dz

--oo

× | exp [--,7(fp)V2]dT? = M(s) (A-8)

Iz]JDLt/2
The result of the integration with respect to ,? in eq. A-8 is broken into a sum
of two integrals with respect to z, i.e.:
/~(S) = (27fe/DL 1/2)[oT/(fp) 1/2]

x (1 + c~g)A _i exp [vz/2DL -- (fp)l/2 (]z ]/DL1/2)] dz

--oo

or
= (2~-e/DL 1/2) [DT/(fp) 1:2 ]

×(l+°Lg)A(iexp[+{(fP)V2+v/2DL1/2}(z/DI)/2)]dz_

+ , exp [ - - { ( f p ) , n _ v/2DLln}z/DLlnl dz
0

Evaluating the integrals and solving for A gives the result:

A = (fp -- va/4DL)'~l(s) (A-9)
4rreDT (1 + ag)
Inserting appropriate values of h (s) into eq. A-5 and of g(s) into eq. A-9 and
substituting eq. A-5 for p in eqs. A-9 and A-4 gives eq. 26.
252

APPENDIX B -- INVERSION OF SOME IMAGE-SPACE SOLUTIONS

In this appendix we establish several results which are useful in deriving

solutions. We begin by considering the Laplace inversion of an image function
-~1 (s) given by:
Fl(s) -- -?'{El(t)} = s -1 exp [ - - ~ { s +/31 --{J2/(s -it- ~ 3 ) } 1/2 ] (B-l)
where ~1,/32, and/33 are constants, and ~3 4:0. We define a function F2(s) by:
F2(s) ~- exp [--~7(s +/31) 1/2]

It is clear that Fl(s) has the form:

~ ( s ) = s-~F2[s-~2/(s + t33)1
Then it can be shown (see Append_ix C) that the original function F l ( t )
corresponding to the image function FI (s) is given by:
t
E l (t) - - ~ -1 {_P~(s)} = J F2(r)F3(t--r, r) dr (B-2)
0
where
F2(t ) = _~ -1 {F2(s)} and F3(t,r ) = . ~ -1 {s-1 exp [~2rl(s +/33)] }
From tables [Erd~lyi, 1954, p. 245, equation 5.6(1)], we find:
F2(t ) = exp (--~lt).9~-l{exp (-- ~7sl/2)}
= [~7/2(~t3) v2 ] exp (-- {Jl t -- ~72/4t) (B-3)
To find F3(t,r), we write:
1

exp [fl2r/(s + ~3)1 ]

F3(t,r) = y-i t(1 + ~31S) (B-4)
[ s+~3
J
We have from tables (Erd~lyi, 1954, p. 245, equation 5.5 (25)] :

= exp (--[J3t)Io [2((J2rt) 1/2 ] (B-5)

where In (x) is the modified Bessel function of the first kind of order n having
argument x. Then, using the result eq. B-5 and the convolution property,
eq. B-4 becomes:

F3(t,r ) = exp (-- ~3 t)Io [ 2(fl2rt) 1/2 ]

t

+ f13 f exp (-- f13 ~)I0 [2(~2T~) 1/2 ] d~ (B-6)

0
 253

The integral in eq. B-6 is related to the function J ( x , y ) which was introduced
by Anzelius (1926) and has been discussed by Goldstein (1953), Masters
(1955), and Luke (1962). The function J ( x , y ) is defined by:

J(x,y) = 1 -- exp (-- y) ~ exp (-- O)Io [2(yo) I/2 ] do (B-7)

0
It has the property:
1 -- J(x,y) = J(y,x) -- exp (-- x -- Y)Io [2(xy) 1/2 ] (B-S)
If the following substitutions are made in eqs. B-7 and B-8:
X = 33t; Y = 32r/33; o = 33~
then it is easily shown that eq. B-6 is equivalent to:
F3(t,r) = exp (32r/33)J(32r/33,33t) (B-9)
We now substitute eqs. B-3 and B-9 into eq. B-2 to obtain:
t
Fl(t) = ½r~Tr-1/2 J exp [--~/2/4T- (31 - - 3 2 / 3 3 ) T]
0
x J[32r/33,33(t -- r)] r-3ndr (B-10)
The image, Fl(S), of F l ( t ) is given by eq. B-1.
In the special case when 33 = 0, eq. B-6 becomes simply:
F3(t,r) = Io[2(32rt)1/21
and eq. B-10 becomes:
t
FI(t)L~3= 0 = ½,r/,fl--1/2 f exp (-- r12/4r -- 31r)I o [2 {32r(t -- r)} in ] r - 3/2dr
0 (B-11)
Next we consider inversion of the image function:
F4(s) = exp [-- 7?{s + 3 1 - - 32/(s + 33)} 1/2]
We note that:
_~4(S) : 8El(8 ) : s.~{Fl(t)} (B-12)
Using the rule for transforming the derivative,

"?'(-~t Fl(t)} =s'~{Fl(t)}-F~(O)

From eq. B-10, F I ( 0 ) is zero, so eq. B-12 becomes:

F4 i s) ~- - ~ ~ Flit)
254

and

.~Q¢-I {"~4 (S)} = ~-~ F 1(t)

We perform the indicated differentiation on eq. B-10, using Leibniz' rule

(Boas, 1966, p.162) and the following properties of the function J ( x , y )
(Goldstein, 1953):
J(x,0) = exp(--x)
0
~Y J ( x , y ) = e x p ( - - x - - y ) ( x / y ) l / 2 I i [ 2 ( x y ) 1/2]

The result is:

. ~ - l ( e x p [--r/{s + 3 , - - 3 2 / ( s +r /33)}'/2])
/ 2 ( T r t a ) l /=2 t exp(--r12/4t--31t)

+ ½r~(32/rr) 1/2 exp (-- 33 t) f exp [-- "02/4r -- (31 -- 33)rl

0
x 11 [2{32r(t -- r ) } l n l r - ' ( t -- r) -1/2 dr (B-13)
The results, eqs. B-10, B-11 and B-13 have been used to invert some image-
space solutions.
Thus to invert Q in eq. 31 we n o t e that:

s+X+k2

= exp [-- (X + k2)t ]

× -~-1{s-1 exp [ - - ~ ( s + v2/4DL + ~ k l - - k 2 - - ~ k l k : / s ) l / 2 ] }
Then, using eq. B-11 with:
31 = v2/4DL + a k l - - k 2 ; 32 = Otklk2; 33 = 0
the result eq_33 follows.
To invert C in eq. 38, we use eq. B-11 with 7? replaced by ~?B1/2 , and:
31 = v 2 / 4 D L B - - 7 ; 32 = Ha = 0
to obtain:
C = (B/~3DL) 1/2 (mo/SDTe) exp [-- (7 + X)t + vz/2DL]
t

x ~ exp [-- (rl2/4r)B -- (v2/4DLB - - 7 ) r ] r -3/2 d r (B-14)

0
We make the substitution u = r-1/2 for r in the integral above. T h e n we use
 255

the following indefinite integral given by Gautschi (1964, p.304, equation

7.4.33), valid for a ¢ 0:

f exp ( - a 2u 2 -- b2/u 2) du = 0 r l n / 4 a ) [exp (2ab) erf (au + b/u)

+ exp (-- 2ab) erf (au -- b/u)] + constant

The result (eq. 39) follows.
To invert C in eq. 40, we note that:

.~_l lexp [--~7(s -}- k + v2/4DL + O~kl --O~klk:/(s T k T k2)}l/2] }

s+~,+7

exp [-- (h + 7 ) t ]
X -~ -1(8-1 e x p [ - - ~?{s + v2/4DL + ak I - - 7 - - a k l k 2 / ( s + k: --7)} 1/2 ] }
Then we use eq. B-10 with:
31 =- v2/4DL + a k l - - 7 ; 32 = a k l k 2 ; 33 = k 2 - - 7
and the result_(eq. 42) follows.
To invert Q in eq. 41, we note that:

£#-1 [exp [-- r/{s + k + v2/4DL + akx - - a k l k ~ / ( s + k + k2)} t/2 ]

( (8 + ;~ + 7 ) ( 8 + ), + k : )

[exp {-- (7 + k)t}/(k2 - - 7 ) ]

x -~ - l {8- 1 exp [-- ~?{s + v2/4DL + ak i -- 7 -- aklk2 (s + k: -- 7) }1/2] }
-- [exp (-- (k2 + k ) t } / ( k : - - 7 ) ]
x . ~ -I{s- l exp [-- 77(s + v:/4DL + a k l --k2 - - a k l k 2 / s ) 1/2 ] }
Then using eq. B-10 with:
(Jl -: v2/4DL + (Xkl - - 7 ; 32 = olklk2 ; 33 = k 2 - - 3 '
and eq. B-11 with:
31 = v2/4DL + olkl --k2 ; 3: = ~ k l k 2 ; 33 = 0
the result (eq. 43) follows.

APPENDIX C -- A RULE FOR INVERSION OF CERTAIN IMAGE FUNCTIONS

We address the following problem. Given an image function/~l(S) which is

the Laplace transform of a k n o w n function F l ( t ) , and given functions gl(s)
and g2 (8) such that the function F2 (s), where:
/72 (8) = [exp (-- Tgl(s)}]/g2 (s)
256

is the Laplace t r a n s f o r m of a k n o w n f u n c t i o n F2 (t,~); t h e n find the f u n c t i o n

F3 (t) whose Laplace t r a n s f o r m F 3 (s) is given by:
F3(s) = [-Pl{s + gl(s)}]/g2(s)
F r o m the definitions of FI (s) a n d F2 (s) as Laplace transforms, we have:

El(S) = I exp (--sT)FI(T) dr (C-1)

0
and
ao

(s) [exp {-- Tg 1(S)}]/g2 (S) = J exp (-- sa)F~ (O,T) do (C-2)
0

Eq. C-1 can be regarded also as the definition of the functional form of FI (s);
accordingly, we may write:

F, [s+g,(s)] = ~ exp[--{s+g,(s)}T]F,(T)dT
0

and then:

if3 (s) = f [l/g2 (s)] exp [-- {s + g, (S)}T] F,(T) dT (C-3)

0
Eq. C-3 can be rearranged as:

-P3 (s) -- ; [exp {-- r g l (s)}/g2 (s)] exp (-- sr)F 1(T) d r (C-4)
0

The q u a n t i t y enclosed in square brackets in eq. C-4 is a Laplace t r a n s f o r m

d e f i n e d b y eq. C-2; s u b s t i t u t i o n o f eq. C-2 i n t o eq. C-4 gives:

F3 (s) = exp (-- sr)F 1(r) dr exp (-- so)F2 (a,r) do (C-5)
o o
N o w let a n e w variable of integration t be given by:
t -- r + a or a = t--r
and substitute (t -- r) for a (holding r c o n s t a n t ) in the integral with respect
to a in eq. C-5. T h e n eq. C-5 becomes:

ff3(s) = f F l ( r ) d r exp(--st)F2(t--r,r)dt (C-6)

0 r

In eq. C-6, the integration with respect to t ranges f r o m t = r to t -- ~ in

strips of w i d t h dr, and the integration with respect to r sums these strips
f r o m r = 0 to r = ~ . If we visualize the t---r plane with t h e line r = 0 as the
 257

abscissa and the line t = 0 as the o r d i n a t e , we see t h a t the integrations in

eq. C-6 cover a wedge-shaped area in the first q u a d r a n t o f t h e plane, this area
lying b e t w e e n the abscissa t = 0 and the line T = t. We n o w a d o p t a proce-
d u r e used b y Boas ( 1 9 6 6 , pp. 6 0 8 - - 6 0 9 ) and reverse the o r d e r o f integration.
We n o w integrate first with r e s p e c t t o • so t h a t this i n t e g r a t i o n ranges f r o m
T = 0 to T = t in strips o f w i d t h dr, and t h e s e c o n d i n t e g r a t i o n with r e s p e c t
t o t sums these strips f r o m t = 0 t o t = oo; this p r o c e d u r e covers the same
area in the t--T plane t h a t was c o v e r e d b y t h e integrations in eq. C-6. T h e
n e w d o u b l e integral is:

-f3(s) = f_ e x p ( - - s t ) Fl(r)F2(t--r,r)dr dt (C-7)

0 0
We r e c o g n i z e eq. C-7 as t h e Laplace t r a n s f o r m o f the q u a n t i t y e n c l o s e d in
brackets. ( C o m p a r e eq. C-1.) T h e r e f o r e :
t

F3 (t) = . ~ - t {~1 [s + g~(s)l/g2(s)} = J F : ( r ) F 2 ( t - - r , r) dr

o
where
Fl(t) = - ~ - l {-P: (s)} and F2(t,r) = - 9 ° - l { e x p [--rgl(s)]/g2(s)}
As an e x a m p l e o f a p p l i c a t i o n o f the m e t h o d , we shall derive a k n o w n ,
general inversion f o r m u l a . L e t F : (s) be t h e t r a n s f o r m e d image o f a f u n c t i o n ,
Fl(t), and let g l ( s ) = g2 (s) = s In . T h e n b y o u r p r o c e d u r e :
F2(t,r) = . ~ - l { e x p (-- rsXn)/sl/2 } = (rrt)- 1/2 e x p (-- r2/4t)
w h e r e we have used a result given b y Erd~lyi [ 1 9 5 4 , p . 2 4 6 , e q u a t i o n 5 . 6 ( 6 ) ]
f o r the inversion. It follows t h a t :
t

- ~ - I { F I ( s + sl/2)/s In } = 7r-1/2 j- F:(r) e x p [-- r2/4(t -- r ) l (t -- r) -1/2 d r

0
(c-8)
The result (eq. C-8) is also given by Erd~lyi [1954, p. 227, equation 5.1(3)].

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