th
International Conference of
International Association for Computer Methods and Advances in Geomechanics (IACMAG)
16 October, 2008
Goa, India
Analysis of Spatial Moments for Reactive Transport through
Fracture  Porous Matrix System
Pramod Kumar Sharma
Dept. of Civil Engineering, M.M.M. Engineering College, Gorakhpur273010 (UP), INDIA
Rajesh Srivastava
Dept. of Civil Engineering, I.I.T. Kanpur208016 (UP), INDIA
Keywords: Fracture media; Reactive transport; spatial moments.
ABSTRACT: We investigate transport of chemicals in fractures affected by firstorder mass transfer, equilibrium
sorption, firstorder reverse sorption, matrix porosity, groundwater velocity and fracture spacing. An advective
dispersive reactive transport equation is used, which accounts for both physical and chemical nonequilibrium. It
was observed that increase in matrix diffusion coefficient reduces the mean displacement of solute in fracture.
Increase in firstorder mass transfer coefficient, reverse sorption coefficient, equilibrium sorption and matrix
porosity reduce the mean displacement and spreading of solute in fracture. As expected, higher value of ground
water velocity and fracture spacing increase the mean displacement and spreading of solute.
1 Introduction
Over the past few decades it has been realised that a significant number of groundwater contaminants are
reactive in nature. The transport of these reactive chemicals in fractureporous matrix involves, in addition to
advection, diffusion, and dispersion, various other mechanisms like ratelimited sorption and desorption,
biodegradation and chemical reaction. Several mathematical models have been developed by various
investigators (Valocchi, 1985; Goltz & Roberts, 1996; Abulaban & Nieber, 2000) to simulate the transport
process. An advective dispersive reactive transport model developed by Brusseau et al. (1989) accounts for
multiple sources of nonequilibrium. Processes responsible for nonequilibrium are divided into two parts. The first
part, which is transport related, is called physical nonequilibrium, and the second part, which is sorption related, is
called chemical nonequilibrium. The physical noneqilibrium is caused by the smallscale heterogeneity of the
porous media, for example in aggregated soils, and affects the transport of both nonsorbing and sorbing solutes.
The chemical nonequilibrium is caused by ratelimited interactions between the solute and specific sorption sites
of the sorbent and affects only sorbing solutes. Only a few studies have been conducted to investigate the
behaviour of reactive chemicals in fracture  porous matrix system, which is an important and complex geological
process. Contaminant behaviour in fracture and matrix for continuous input condition was analysed using the dual
porosity approach by Tang et al. (1981). Sudicky & Frind (1982) developed analytical solutions for radioactive
contaminant transport in a system of multiple discrete parallel fractures. Kennedy and Lennox (1995) used control
volume approach for modelling solute transport through fracture in a porous matrix. Durham et al. (2001) carried
out experiments to examine the relationship between local rate of dissolution and local aperture during flow of
acidic aqueous solution through a rough fracture. West et al. (2004) derived analytical solutions for a system of
evenly spaced, parallel discrete fractures to simulate solute transport in both the fracture and the contiguous
porous matrix. Suresh Kumar & Sekhar (2005) presented numerical analysis of spatial moments for nonreactive
solute transport through fracturematrix system. We analyze the transport process in fractureporous matrix
system and evaluate the effect of various factors, i.e. firstorder mass transfer, equilibrium sorption, firstorder
reverse sorption, matrix porosity, groundwater velocity in fracture, and fracture spacing on the plume behavior
2 Governing Equations
Figure 1a shows a fracturematrix system and Figure 1b depicts the movement of a chemical in fracture. The
transport processes in fracturematrix system is described by two coupled equations, one for fracture and the
other for the porous matrix. The groundwater velocity in the fracture is assumed constant, and a solute source of
constant strength is assumed to exist at the inlet of the fracture. Tang et al. (1981) showed that the coupling
between the fracture and porous matrix is represented by the continuity of fluxes and concentration along the
interface. It is also assumed that diffusive flux from fracture to porous matrix takes place perpendicular to the
fracture, and complete mixing across the fracture width takes place at all times. For porous matrix Brusseau et al.
(1992) developed general transport equations that account for both the physical and chemical nonequilibrium.
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This advectivedispersivereactive transport equation for transport through the advective region of a porous
matrix can be written as:
( ) ( )
2 2
2
2 2
2 2
C S C C C
a a a a a
f F K f D D q C C
a a a a n
a L a m
t t x
x y
f F K C f S
a a al a a
a a a
+ + = +
+
(1)
The mass balance for the nonadvective region can be described by the following equation:
( ) ( ) ( ) ( ) [ ] ( )
2 2
2
1 1 1 ) 1 (
n n n n n nl n n n a
n n
n n n
S f C K F f C C
t
S
f
t
C
K F f + =
+
(2)
where,
a
is the fractional volumetric water content of the advective region (L
0
),
n
is the fractional volumetric
water content of the nonadvective region (L
0
), f is the mass fraction of sorbent constituting the advective region
(M
0
), is the bulk density of the porous medium (ML
3
), , F F
a n
are the mass fraction of sorbent for which sorption
is essentially instantaneous (M
0
), , K K
a n
are the equilibrium sorption coefficient for advective and nonadvective
region (L
3
M
1
), C
a
is the concentration of solute in solution phase for advective region (ML
3
), C
n
is the
concentration of solute in solution phase for nonadvective region (ML
3
), t is the time (T),
2
S
a
and
2
S
n
are the rate
limited sorbedphase concentration in advective and nonadvective regions
1
( ) MM
, x
j
are the coordinate
directions (L),
D
ij
is the hydrodynamic dispersion tensor (L
2
T
1
), q
i
are the specific discharge components (LT

1
), is the firstorder coefficient for mass transfer between the advective and nonadvective regions (T

1
),
a
and
n
are the firstorder transformation coefficient for the solution phase in advective and nonadvective
regions,
1 a
and
1 n
are the transformation coefficients (T
1
) for the instantaneous sorbedphase of advective and
nonadvective regions, respectively, and
2 a
and
2 n
are the transformation coefficients for ratelimited sorbed
phase domains of advective and nonadvective regions, respectively. Subscript a refers to the advective region
and n to the nonadvective region.
Dynamics of sorption and transformation for the ratelimited domains are described by:
2
[(1 ) ]
2 2 2 2
S
a
k F K C S S
a a a a a a a
t
(3)
2
[(1 ) ]
2 2 2 2
S
n
k F K C S S
n n n n n n n
t
(4)
where, k
a2
and k
n2
are the firstorder reverse sorption rate coefficients (T
1
) for the advective and nonadvective
region, respectively.
The transport equation for the fracture media can be written as:
2
2
C C C
D C f f f
a m a
V D
f f
t x b y
x
+ = +
(5)
whereD V D
f f f m
= + ; V
f
is water velocity in fracture (L/T); b is half fracture aperture (L); D
f
is hydrodynamic
dispersion coefficient (L
2
/T); D
m
is effective molecular diffusion coefficient (L
2
/T);
f
is longitudinal dispersivity in
the fracture (L); and y is the transverse spatial coordinate (L).
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Figure 1a. Fractureporous matrix system.
Figure 1b. Movement of solute in fracturematrix system.
3 Numerical model and validation
An implicit finitedifference technique has been used for the solution of the transport equations (Equations 15).
The following initial and boundary conditions are used:
( ) ( )
( )
0
,
,0 0; 0, ; 0
f f
t
C
f
C x C t C
x
= = =
(6)
( ) ( ) ( )
( ) , ,
, ,0 0; , , , ; 0
a a f
x L t
C
a
C x y C x b t C x t
y
= = =
(7)
( ) ( ) ( )
2 2
, ,0 0; , ,0 0; , ,0 0
n a n
C x y S x y S x y = = = (8)
where,
0
C is initial injected concentration of solute source at the inlet of the fracture (M/L
3
).
For validation of the model, spatial moments of solute in fracture are computed with input parameters listed in
b
X
Y
0 =
x
C
a
0 =
y
C
a
0
C C
f
=
L
L
1
X
Porous matrix
Surface sorption
Diffusion in
fracture
Solute
concentration
Y
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Table 1 and compared with results of Suresh Kumar & Sekhar (2005). Temporal variation of first moment is
shown in Figure 2. The mean travel distance is nonlinear during early time and increases linearly with increasing
time. For large time the behavior of first moment is similar to that of a conservative solute in a homogeneous
porous media. During early times, the velocity of the center of mass decreases with time indicating an increase in
retardation. Also, the mean displacement decreases with increasing value of matrix diffusion coefficient. As
expected, larger matrix diffusion coefficient enhances the mass flux loss from the fracture into the porous matrix.
The qualitative behavior of solute displacement remains same for different matrix diffusion coefficients and is
characterized by three regions. In the first region (early time) mean displacement is due to front movement in the
fracture with little influence of the matrix. The velocity is the same as injected water velocity. In the second region,
the mass flux from fracture to matrix dominates the system and the displacement curves diverge from one
another for different matrix diffusion coefficients. In the third region (large time) the displacement is linear and
fracture and matrix act as a single unit. This equilibrium is reached early for larger matrix diffusion coefficients.
Table 1. Input Parameters for the Fracture
Parameter Value Parameter Value
Injected fracture velocity,V
f
1.0 m/d Halffracture spacing, L 0.01 m
Local fracture velocity,
f
0.5 m Porosity (matrix) 0.01
Halffracture aperture, b 50.E06 m
Table 2. Input Parameters for Porous Matrix
Parameter Value Parameter Value
2.00 g/mL 0.01 d
1
a
0.01 ka2 ( =kn2) 0.3 d
1
n
0.01 V 0.1 m/d
f 0.5 Longitudinal dispersivity,
L
0.5 m
Fa ( =Fn) 0.5
1 2 1 1 a a a n n n
= = = = = 0.0 d
1
Ka ( =Kn) 0.15 mL/g Dm 1.E06 m
2
/d
0 10 20 30 40 50
0
10
20
30
40
50
1E04
1E06
D
m
=1E10m
2
/day
F
i
r
s
t
m
o
m
e
n
t
(
m
)
Time(days)
Resultsof SureshKumar. G., andSekhar, M.
Numerical results
Figure 2. First moment of ideal solute in fracture for different matrix diffusion coefficients.
4 Spatial moments for reactive plume
The model was used to predict the spatial moments with the input parameters listed in Tables 1 and 2. Figure 3
shows the moments for different values of mass transfer coefficient (which represents the interaction between the
solution phases of advective and nonadvective domains). During early time the mean displacement is nonlinear
and increases linearly for large time. With an increase in the mass transfer coefficient the mean displacement
decreases. The concentration of solute in porous matrix reduces with increase in the value of firstorder mass
transfer coefficient. The mean displacement of solute in fracture is similar to reactive transport in porous media.
The spreading is nonlinear for small travel time and becomes linear for large travel time. The variance decreases
with increase in the mass transfer coefficient at large travel time, while it remains same for small time. The matrix
diffusion causes additional spreading of solute at large time. The spreading of solute in fracture for large time is
similar to reactive transport through porous media.
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0 25 50 75 100 125 150 175 200
0
5
10
15
20
25
30
1.0
0.0
F
i
r
s
t
m
o
m
e
n
t
(
m
)
Time(days)
0 25 50 75 100 125 150 175 200
0
50
100
150
200
250
300
350
400
1.0
0.0
S
e
c
o
n
d
m
o
m
e
n
t
(
m
2
)
Time(days)
(a) (b)
Figure 3. Spatial moments of solute in fracture (a) First moment (b) Second moment. Numbers near the curve
represent value of mass transfer constant in d
1
.
Figure 4 shows the evolution of mean displacement and spreading of solute in fracture for different equilibrium
sorption coefficients. During early stage, the mean displacement is non uniform and it is linear for large time.
Larger equilibrium sorption coefficient reduces the mean displacement and it remains constant for large time.
During early stage, the value of mean displacement is same for both values of equilibrium sorption. For lower
sorption, mean displacement is similar to transport of solute in porous matrix. Similarly, the spreading of solute is
non linear at early time and decreases with increase in equilibrium sorption. Also, the variance is very small at
early stage of transport.
0 25 50 75 100 125 150 175 200
0
10
20
30
40
50
60
70
1.0
0.0
F
i
r
s
t
m
o
m
e
n
t
(
m
)
Time(days)
0 25 50 75 100 125 150 175 200
0
100
200
300
400
500
600
700
800
1.0
0.0
S
e
c
o
n
d
m
o
m
e
n
t
(
m
2
)
Time(days)
(a) (b)
Figure 4. Spatial moments of solute in fracture (a) First moment (b) Second moment. Numbers near the curve
represent the value of equilibrium sorption coefficients K
a
(=K
n
) in mL/g.
Figure 5 shows the mean displacement and spreading of solute in fracture for different firstorder sorption
coefficients. Mean displacement is non uniform during early stage and increases linearly with time. Larger first
order sorption coefficient reduces the mean displacement for large time and it remains same during early stage.
The effective velocity during early stage is larger for lower rate coefficient. For larger times, the effective velocity
approaches its asymptotic value corresponding to the equilibrium sorption. The spreading is also non uniform for
small time and increases linearly at large time. Larger firstorder coefficient reduces the spreading of solute at
large time.
0 25 50 75 100 125 150 175 200
0
5
10
15
20
25
30
1.0
0.0
F
i
r
s
t
m
o
m
e
n
t
(
m
)
Time(days)
0 25 50 75 100 125 150 175 200
0
50
100
150
200
250
300
350
0.0
1.0
S
e
c
o
n
d
m
o
m
e
n
t
(
m
2
)
Time(days)
(a) (b)
Figure 5. Spatial moments of solute in fracture (a) First moment (b) Second moment. Numbers near the curve
represent the value of first order sorption coefficients k
a
(=k
n
) in d
1
.
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The first spatial moment and spreading of solute for different porosity of matrix is shown in Figure 6. The mean
displacement is non uniform during early stage and is linearly increasing at large time. Mean displacement
decreases with increase in matrix porosity. The spreading of solute in fracture is small for large value of porosity
at large travel time. Thus higher value of matrix porosity reduces the solute concentration in fracture with increase
in time, while solute concentration increases in the porous matrix.
0 25 50 75 100 125 150 175 200
0
5
10
15
20
25
0.1
0.01
F
i
r
s
t
m
o
m
e
n
t
(
m
)
Time(days)
0 25 50 75 100 125 150 175 200
0
50
100
150
200
250
0.1
0.01
S
e
c
o
n
d
m
o
m
e
n
t
(
m
2
)
Time(days)
(a) (b)
Figure 6. Spatial moments of solute in fracture (a) First moment (b) Second moment. Numbers near the curve
represent the value of matrix porosity ( )
a n
= .
0 25 50 75 100 125 150 175 200
0
10
20
30
40
50
1.0
2.0
F
i
r
s
t
m
o
m
e
n
t
(
m
)
Time(days)
0 25 50 75 100 125 150 175 200
0
100
200
300
400
500
600
700
800
900
1000
1.0
2.0
S
e
c
o
n
d
m
o
m
e
n
t
(
m
2
)
Time(days)
(a) (b)
Figure 7. Spatial moments of solute in fracture (a) First moment (b) Second moment. Numbers near the curve
represent the value of groundwater velocity in fracture in m/d.
0 50 100 150 200
0
20
40
60
80
100
0.01
0.1
F
i
r
s
t
m
o
m
e
n
t
(
m
)
Time(days)
0 50 100 150 200
0
200
400
600
800
1000
0.01
0.1
S
e
c
o
n
d
m
o
m
e
n
t
(
m
2
)
Time(days)
(a) (b)
Figure 8. Spatial moments of solute in fracture (a) First moment (b) Second moment. Numbers near the curve
represent the value of half  fracture spacing in m.
Figure 7 shows the effect of velocity in fracture. Larger velocity increases the mean displacement of solute at
large time. It indicates that the movement of solute in fracture increases with increase in velocity. During early
stage, the spreading of solute in fracture is small and non uniform, and linearly increases at large time. Larger
velocity increases the spreading of solute in fracture at large times. The transport of solute in fracture at large
time is similar to that in porous matrix.
The effect of fracture spacings is shown in Figure 8. Larger halffracture spacing increases the mean
displacement at large travel time implying that solute concentration increases in fracture with increase in fracture
spacing. During early stage, the spreading is small and non uniform, and increases linearly at large time. For
2461
large fracture spacing, the spreading of solute increases at large time. The transport of solute at large time is
similar to solute transport in porous matrix.
5 Concluding remarks
We investigate the effect of various sorption coefficients, porosity of matrix, groundwater velocity and half fracture
spacing on spatial moments for solute transport through fracturematrix system. It was observed that higher
matrix diffusion decreases the mean displacement of solute in fracture with increase in time. The mean
displacement is nonuniform during early stage of transport and it becomes linear for large times. Increase in first
order mass transfer coefficient, reverse sorption coefficient, equilibrium sorption, and matrix porosity reduce the
value of mean displacement and spreading in fracture. Higher value of velocity and fracture spacing increase the
value of mean displacement and spreading of solute with increase in time. Finally, it was observed that the
behavior of solute in fracture is similar to the solute transport in porous media for large travel times.
6 References
Abulaban, A., Nieber, J .L. 2000. Modeling the effects of nonlinear equilibrium sorption on the transport of solute plumes in
saturated heterogeneous porous media, Advances in Water Resources, 23, 893905.
Brusseau, M.L., J essup.R.E., Rao, P.S.C. 1989. Modelling the transport of solutes influenced by multiprocesses
nonequilibrium. Water Resources Research, 25(9), 19711988.
Brusseau, M.L., J essup.R.E., and Rao, P.S.C. 1992. Modelling the transport of solutes influenced by multiprocesses
nonequilibrium and transformation reactions. Water Resources Research, 28(1), 175182.
Durham, W.B., Bourcier, W.L., Burton, E.A. 2001. Direct observation of reactive flow in a single fracture. Water Resources
Research, 37(1), 112.
Goltz, M. N., Roberts, P.V. 1996. Threedimensional solutions for solute transport in an infinite medium with mobile and
immobile zones, Water Resources Research, 22(7), 11391148.
Kennedy, C.A., Lennox, W.C. 1995. Acontrol volume model of solute transport in a single fracture. Water Resources Research,
31(2), 313322.
Sudicky, E.A., Frind, E.O. 1982. Contaminant transport in fracture porous media: Analytical solutions for a system of parallel
fractures. Water Resources Research, 18, 16341642.
Suresh Kumar, G., Sekhar, M. 2005. Spatial moment analysis for transport of nonreactive solutes in a fracturematrix system.
Journal of Hydrologic Engineering, ASCE, 10(3), 192199.
Tang, D.H., Frind,E.O., Sudicky, E.A. 1981. Contaminant transport in fracture porous media: Analytical solution for a single
fracture. Water Resources Research, 17, 555564.
Valocchi, A.J . 1985. Validity of the local equilibrium assumption for modeling sorbing solute transport through homogeneous
soils. Water Resources Research, 21(6), 808820.
West, M.R., Kueper, B.H., Novakowski, K.S. 2004. Semianalytical solutions for solute transport in fractured porous media
using a strip source of finite width. Advances in Water Resources, 27, 10451059.
Xu, S., Worman, A. 1999. Implications of sorption kinetics to radionuclide migration in fractured rock. Water Resources
Research, 35(11), 34293440.
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