Subsurface Flow and Transport: Mariush W. Kemblowki and Gilberto E. Urroz

4.
1 INTRODUCTION
This chapter begins with the mathematical description of the constitutive relationships for
flow and transport in porous media. Following this, simple analytical solutions are pre-
sented for a variety of subsurface flow and transport problems. The principles of flow and
transport are outlined, and solutions are provided for practical problems of flow and trans-
port in both the saturated and the unsaturated zones. The latter includes problems of
transport in the vapor phase. The major focus is on the processes that are relevant to
subsurface mitigation.
4.2 CONSTITUTIVE RELATIONSHIPS
This section presents the basic concepts and laws used to describe flow and transport in the
subsurface. In particular, the constitutive relationships defining the fluid flow in fully and
partially saturated media are given as well as the relationships that describe diffusive and dis-
persive mass fluxes in porous media. Finally, we show the relations used to describe parti-
tioning of chemicals in the subsurface environment.
4.2.1 Darcys law
Consider the flow of a fluid through a pipe filled with a granular material, as shown in Fig.
4.1. In the figure, z
1
and z
2
represent the elevations of the pipe centerline above a reference
level at Sections 1 and 2, respectively, whereas p
1
/ and p
2
/ represent the water
pressure head at Sections 1 and 2, respectively. We define the piezometric head at any
location in the porous media as
h z p/ (4.1)
where specific weight (weight per unit volume) of water, typically, 9810 N/m
3
or
62.4 lb/ft
3
. Let q be the average water velocity in the cross section of the pipe: i.e.,
q Q/A (4.2)
CHAPTER 4
SUBSURFACE FLOW
AND TRANSPORT
Mariush W. Kemblowki and Gilberto E. Urroz
Utah Water Research Laboratory
Utah State University
Logan, Utah
4.1
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Source: HYDRAULIC DESIGN HANDBOOK
where Q volumetric discharge (volume per unit time) and A total cross-sectional area
of the pipe (including the soil matrix). French hydrologist Henry Darcy discovered that
the average flow velocity could be estimated from
q K (h
1
h
2
)/L (4.3)
where L is the distance, measured along the pipe, between cross sections 1 and 2, and K
is a parameter that depends on the nature of the porous media as well as on the properties
of the transported fluid. For water, K is known as the hydraulic conductivity or the coef-
ficient of permeability. Typical values of K are given in many references (e.g., Bureau of
Reclamation, 1985) see tables 4.1 ard 4.2. Eq. (4.3) is known as Darcy's law and is com-
monly used to model the flow of fluids in porous media. Notice that the velocity V is not
the fluid velocity in the soil pores, it is an average velocity calculated over the entire area
of the flow cross section. The average pore velocity is calculated as
v
q
W
(4.4)
where
W
is the volumetric water moisture content. Note that for saturated flow,
W
n,
where n is porosity.
Darcys law (i.e., Eq. 4.3) also can be written more concisely as
q KI (4.5)
where I is the hydraulic gradient defined as
I
(h
1
L
h
2
)
4.6)
Hydraulic conductivity K is a function of aquifer and fluid properties specifically of
the intrinsic soil permeability k, fluid viscosity , and fluid density and is given by
K k g/ (4.7)
For saturated flow of a constant density fluid in isotopic porous media, the Darcy law
can be written as
4.2 Chapter Four
FIGURE 4.1 Porous media flow.
Arbitrary datum
h
1
z
1
1
2
h
2
z
2
p
w
2
p
w
1
h
L
SUBSURFACE FLOW AND TRANSPORT
q
i
K
,
(4.8)
For anisotropic media, the Darcy law is written as
q
i
K
ij
x
h
j
,
(4.9)
where K
ij
is the conductivity tensor. For saturated flow of a fluid of variable density in
anisotropic porous media, we have
q
i

s
f
o
lu
il
i
,
d
ij
x
p
i

fluid
g
x
z
i
,
(4.10)
where k
soil,ij
is the intrinsic permeability tenser. Finally, for unsaturated flow of variable-
density fluid in anisotropic porous media, we have
q
i

k
r
(
)
fl
k
ui
s
d
oil,ij
x
p
j

fluid
g
x
z
j
,
(4.11)
where k
r
() relative permeability of the porous media. Relative permeability is a func-
tion of soil saturation, which in turn is a function of the capillary pressure. These rela-
tionships for partially saturated flow are discussed in the next section.
4.2.2 Unsaturated FlowConstitutive Relationship
In unsaturated flow, the concern is water movement in the zone above the water table. In
this case, the water saturation S
w
is a function of the difference between air and water
pressures because the water is resulting from held by capillary forces resulting from sur-
face tension. This difference is known as the capillary pressure and is defined as
h
aw
h
a
h
w
(4.12)
Typically, in unsaturated flow theory we assume negligible resistance to the gas-phase
flow in porous media; as a result, we also can assume that the gas-phase pressure is uni-
form and equal to the atmospheric pressure. Hence h
aw
h
w
. The aqueous pressure in
the unsaturated zone is lower than the atmospheric pressure; thus, the capillary pressure
is positive. The negative pressure head h
w
also is known as the soil matrix suction . Thus,
the total head in the aqueous phase is h + z.
To remove water from the pore space i.e., to reduce the water content we have to apply
more negative pressure to the aqueous phase, i.e., increase the capillary pressure h
aw
. This
relationship is typically called the soil-water retention curve, and can be expressed by the
following commonly used parametric models: the Brooks-Corey (BC) model and the van
Genuchten (VG) model. The BC model is
r
r
(4.13)
for h
b
and is otherwise (capillary fringe zone),
e
1 (4.14)
where n porosity, volumetric moisture content (equal to n S
w
),
e
effective volu-
metric moisture content,
r
residual (irreducible) moisture content, Brooks-Corey
parameter, and h
b
capillary fringe height. The van Genuchten model is
h
x
j
Subsurface Flow and Transport 4.3
n
r

r
[1 ()
n
]
m
(4.15)
where: n curve fitting parameter that depends on the type of soil, soil property
index, 1/h
b
, and m 1 1/n.
Note that parameter n depends on pore-size distribution. For a well-graded soil (wide
pore-size distribution, which results in a flatter moisture content curve ()), n is small,
whereas for poorly graded soils (narrow pore-size distribution, which results in a steeper
moisture content curve (), n is large: typically values of n higher than 2.5.
Also note that although the BC and VG models are the most commonly used models
in analysis, there is no restriction on using different mathematical representations to
describe the characteristics of soil-water retention. For example, a simple exponential
model, such as
e
exp( ), is in some cases, sufficient to describe the physics of the
retention.
As the moisture content in partially saturated media decreases, so does the volume of
pores available to fluid flow. Thus, hydraulic conductivity for the partially saturated media
depends on the water content and, in turn, on the metric suction. To describe this rela-
tionship, we modify the value of intrinsic permeability k by the factor of k
r
() or k
r
(),
called relative permeability. Several models for k
r
are shown below:
BC model of relative permeability:
k
r
(4.16)
VG model of relative permeability:
k
r
e
0.5
(1 (1
e
1/m
)
m
)
2
(4.17)
Mualem model of relative permeability:
k
r
exp [ ] (4.18)
4.2.3 Diffussive and Dispersive fluxes
4.2.3.1 Molecular diffusion. Molecular diffusion describes the process by which a con-
taminant species dissolved in an environmental fluid moves from regions of higher
concentration to regions of lower concentration. When the only mechanism affecting the
diffusion of the contaminant species is the random motion of its molecules, the process is
referred to as molecular diffusion. The mass flux of a solute along a single direction, in a
liquid or gaseous body, is described by Fick's law:
q D
d
d
C
x
(4.19)
In this equation, q mass flux of solute per unit area per unit time [ML
2
T
1
],
D diffusion coefficient (L
2
T
1
), C solute concentration mass of solute/volume of
solution (M/L
3
), dC/dx concentration gradient along the x direction. The minus sign in
Eq. (4.19) indicates that the solute flux will go from regions of larger concentration to
those of lower concentration. Values of the diffusion coefficient, D, depend on the type of
solute and the type of environmental fluid. For major cations and amnions dissolved in
water, values of D range from 1 10
9
to 2 10
9
m
2
/s (Fetter, 1994).
4.4 Chapter Four
4.2.3.2 Molecular diffusion in porous media Molecular diffusion in a porous medium
is affected by the nature of the medium. For example, the paths that diffusing molecules
follow in a porous medium are, in general, more complicated than if they were diffusing
in water. Although Eq. (4.19) can still be used to describe the diffusion in a porous medi-
um, the diffusion coefficient must be modified, and Eq. (4.19) is rewritten in terms of an
effective diffusion coefficient. One widely accepted expression for the effective diffusion
coefficient in porous media is the Millington-Quirk equation
D D
o
so
n
lu
2
tion
3.33
(4.20)
where D
o
is the molecular diffusion coefficient of the compound in pure solution fluid,
solution
is the solution fluid-filled porosity of the soil, and n is the total porosity of the soil.
4.2.3.3 Mechanical dispersion and macro-dispersion. Mechanical dispersion refers to
the component of dispersion caused by differences in velocity at the pore level that are a
consequence of the pore geometry. Water will move at different rates as a result of differ-
ences in pore sizes and tortuosity. A contaminant dissolved in the water flowing through
a porous medium will be dispersed in both the longitudinal and transverse directions
because of the fluctuations in the water velocity field. A way to incorporate the influence
of pore geometry in the dispersion process is to define longitudinal and transverse disper-
sivities
L
and
T
. Longitudinal and transverse mechanical dispersion coefficients can thus
be defined in terms of the dispersivities and the average pore velocity. For example, the
longitudinal mechanical dispersion coefficient (D
L
)
mech
will be given by (D
L
)
mech
L
v.
This dispersion coefficient is not treated separately from the effective diffusion coefficient
defined in (8); instead, they are both combined in a coefficient of hydrodynamic disper-
sion. Thus, Ficks Law, which describes molecular diffusion in a fluid, can be used to
describe longitudinal and transverse dispersion in a porous medium if the diffusion coef-
ficient D in Eq. (4.19) is replaced by a coefficient of longitudinal (or transverse) hydro-
dynamic dispersion, D
L
or D
T
, given by
D
L

L
v D* (4.21)
or
D
T

T
v D* (4.22)
where
L
,
T
longitudinal and transverse dispersivities, respectively, and D* effec-
tive porous-media diffusion coefficient.
In addition to the pore-scale dispersion, we also have formation-scale dispersion or,
more accurately, spreading, which is a result of the variability in transport velocity caused
by the heterogeneity of the hydraulic conductivity field. In terms of magnitude, this
microdispersive flux is significantly larger than the one related to mechanical dispersion.
Mathematically, macrodispersive flux is the flux equal to the expected value of the prod-
uct of Darcian velocity (q) and of the contaminant concentration (C) fluctuations:
q
macrodispersive
q C (4.23)
In otherwords, this flux can be described using an expression similar to the Fickian diffu-
sion equation (Eq. 4.19) with a macrodispersivity coefficient. In the most general (three-
dimensional) case, the equation defining the macrodispersive flux in the flowing fluid is
q
i
( A
ij
v )
x
C
j
(4.24)
where A
ij
represents the macrodispersivity tensor and the bar indicates averaged quanti-
ties. The fluctuations q and c result from the heterogeneous nature of the aquifer. This is
expressed in the way the macrodispersivity tensor is estimated. For example, the longitu-
dinal macrodispersivity is estimated using
A
11
2
2
(4.25)
where
f
2
variance of log-conductivity (f L
n
[K]),
1
correlation scale in the direc-
tion of flow, and is given by

K
q
g
J
1
exp

6
f
2
1
1
]
(4.26)
In summary, the longitudinal and transverse components of the total diffusive and dis-
persive mass flux (per unit bulk area) in heterogeneous geologic formations is estimated
as follows:
q
L
(
FLUID
A
L
v
FLUID
D)
C
x
(4.27)
q
T,HOR
(
FLUID
A
T,HOR
v
FLUID
D)
C
y
(4.28)
q
T,vert
(
FLUID
A
T,vert
v
FLUID
D)
C
y
(4.29)
where D Millington-Quirk effective dispersion coefficient.
4.2.4 Partitioning
Equilibrium partitioning and sorption are the most common chemical processes that
affect reactive transport. These processes are dealt with by equating the total concentra-
tion to the sum of the concentrations in each phase multiplied by their respective volumes.
Furthermore, by equating the concentration in each phase to the concentration in a com-
mon phase say, the concentration in water the total concentration can be expressed in
terms of the common phases concentration and a retardation coefficient R
C
T
WATER
C
WATER
(1
I WATER
K
WA
1
TE
1
R
)
WATER
C
WATER
R
(4.30)
where: K
I
partitioning coefficient between the i
th
phase and the common phase K
I
C
I
/
C
WATER,
I
the volumetric content of the ith phase, and
WATER
the volumetric content
of the common phase. This type of equilibrium partitioning is frequently used to describe
the relationships between concentrations in the following scenarios: (1) vapor and aque-
ous phases, (2) soil and vapor phases, (3) soil and aqueous phases, (4) partitioning of a
tracer between aqueous and NAPL or DNAPL phases, and (5) partitioning of a tracer
between vapor and NAPL or DNAPL phases.
4.6 Chapter Four
For partitioning of compounds present in a NAPL or DNAPL mixture and aqueous
phase, we use
C
I,WATER
x
I
S
I
(4.31)
where S
I
is the solubility of compound I in water and x
I
is its mole fraction in the mixture.
Finally, for partitioning of compounds present in a NAPL or DNAPL mixture and vapor
phase, use
V
i
[mg/L] 10
3
[mg/g]x
i
(4.32)
where V
I
is the vapor concentration of compound I, P
v,I
is the vapor pressure of compound
I, M
W,I
is its molecular weight, R gas constant, and T temperature in K.
4.2.5 Degradation
In addition to partitioning, degradation of compounds also may affect the fate and
transport of reactive compounds significantly. Typically, degradation is modeled using
either power-order decay models or growth-process-based models. In environmental
subsurface hydrology, three basic power-order models are used: (1) zero-order decay,
(2) first-order decay, and (3) a combination of the first two models. According to these
models, the total decrease of mass in unit bulk volume caused by degradation is
expressed by
C
t
T
I PHASES
I
K
0,I
I PHASES
I
K
1,I
C
I
(4.33)
where K
0,I
zero-order degradation rate of the compound in phase I, K
1,I
first-order
degradation rate of the compound in phase I, and C
I
= mass/volume concentration of the
compound in phase I.
In addition to the zero-order and first-order degradation processes, the Monad kinetics
is frequently used to describe oxygen limited aerobic degradation of organic compounds
in the aqueous phase. According to the Monod model, the degradation rate in terms of the
total concentration is expressed by the following system of equations:
C
t
T
WATER
M
t
K
C
C
WA
C
TE
W
R
ATER
K
O
O
W
O
ATE
W
R
ATER
,
(4.34)
and
O
t
T
WATER
M
t
K
C
C
WA
C
TE
W
R
ATER
K
O
O
WA
O
TE
W
R
ATER
,
(4.35)
where C
WATER
is the aqueous concentration of the contaminant, O
WATER
is the dissolved oxy-
gen concentration, M
t
is the total concentration of the active microbial biomass, is the
maximum rate of organic solute utilization, K
C
is the concentration of the organic solute
at which the utilization rate is half the maximum, K
O
is the electron acceptor (oxygen)
concentration at which the utilization rate is half the maximum, and is the substrate uti-
lization ratio.
P
vi
[atm]* M
w,i
[g/mole]
R 0.0821[L atm/mole K]T[K]

4.3 FLOW AND TRANSPORT IN SATURATED ZONES
In this section, we present some solutions to saturated flow and transport problems that
are encountered in the practice of subsurface hydrology. We begin with well hydraulics,
an understanding of which is important to the design of pump-and-treat systems, and dis-
cuss several models of transport of soluble plumes.
4.3.1 Flow to a Single Well
Darcy's law describes the average water flux through a porous medium when the local
hydraulic gradient is known. To determine discharges we use the law of conservation of
mass for the water, also known as the continuity equation. For the analysis of wells, it is
assumed that the flow toward the well caused by the well pumping is radially symmetric.
In this situation, it is convenient to use the equation of continuity in radial coordinates
(r, ). For steady-state state flow toward a single well in a confined aquifer without
recharge, the equation reads
Q 2KB
d
d
h
r
(4.36)
where K and B aquifer conductivity and thickness, respectively. The equation of conti-
nuity for well flow in an unconfined aquifer is similar to Eq. (4.19): namely,
Q 2rKh
d
d
h
r
(4.37)
with B replaced by the variable flow depth h. Implicit in Eq. (4.36) and (4.37) is the
Dupuit-Forchheimer assumption, the implication of which is that the flow in the aquifer
can be assumed to be practically horizontal.
Equations (4.36) and (4.37) are used to obtain solutions for the steady-state discharge
to a well in confined and unconfined aquifers, respectively, if the piezometric heads (con-
fined aquifers) or water-table elevations (unconfined aquifers) h
1
and h
2
are known at two
radial distances r
1
and r
2
, respectively:
Q 2KB(h
2
h
1
)/ln(r
2
/r
1
) 2T(h
2
h
1
)/ln(r
2
/r
1
) (4.38)
where T KB aquifer transmissivity, and
Q KD(h
2
2
h
1
2
)/ln(r
2
/r
1
) (4.39)
The solutions given in Eqs. (4.38) and (4.39) assume that the well penetrates to the
impermeable bottom of the aquifer and that there is no recharge into the aquifer. They also
assume an infinitely large aquifer with no interaction with surface streams or imperme-
able boundaries. Well solutions are often given in terms of the drawdown s as a function
of the radial distance r. The drawdown is defined as
s H h (4.40)
where H is the elevation of the original piezometric surface before pumping at the well
starts. The distance R for which h H and s 0 is called the radius of influence of the
well. Using the concepts of drawdown and radius of influence, the steady-state flow equa-
tion in a confined aquifer can be rewritten as
s
2
Q
T

Ln
R
r
1
1
]
(4.41)
4.8 Chapter Four
By combining the solutions for the steady state flow in confined and unconfined
aquifers, one can derive a relationship between the drawdown calculated from confined
conditions (assuming constant in space and time aquifer thickness equal to H), and that
estimated for unconfined conditions (when the change in aquifer thickness caused by
pumping is taken into account):
s
UNC
H H
2
2 s
C
ON
F
H (4.42)
Using this formula, known as Jacobs correction, one can initially assume constant
aquifer thickness B H in calculations and use confined aquifer solutions to calculate
drawdown, then correct the drawdown using Jacobs correction. This approach is particu-
larly useful when dealing with transient flow. For transient flow conditions in an aquifer
with constant flow thickness, the transient drawdown is given by
s (r,t)
4
Q
T

exp[
x
x]
dx
4
Q
T
W [u(r,t)] (4.43)
where
u(r,t)
4
r
2
T
S
t
(4.44)
and S storativity (for confined aquifers) or porosity (for unconfined aquifers) and W(u)
is known in subsurface hydrology as well function and in mathematics as exponential inte-
gral. This function is tabulated in almost every groundwater hydrology textbook. It also is
available in many engineering mathematics software packages, such as Mathematica, as
a library function.
4.3.2 Superposition and Convolution
For a time-variable pumping rate, the principle of convolution can be used to estimate the
transient drawdown. This approach is strictly valid for linear systems: i.e., systems in
which the response (drawdown) is a linear function of the excitement (pumping rate). The
linearity assumption is strictly valid for confined aquifers only; however, as long as the
drawdowns do not exceed 20% of the initial aquifer thickness, it also may be used for
unconfined aquifers. Using the convolution approach, the transient drawdown for a pump-
ing rate changing in a step-wise fashion is given by
s(r,t)
4
1
T

n
k 1
(Q
K
Q
K 1
)W(u(r,t
K 1
)) (4.45)
where the drawdown is estimated at time t, t
n
t t
n 1
, Q
K
is the pumping rate for
t
K 1
t t
K,tO
0, Q
0
0.0, and t
K 1
t t
K 1
. When several wells are present,
the superposition approach is used to estimate the cumulative drawdown by adding the
drawdown contributions from all the wells:
s(t)
4
1
T

m
L 1
Q
L
W(u(r
L
,t)) (4.46)
where r
L
is the distance between the point of interest (where the drawdown is estimated) and
well L. When several wells are pumping at variable rates, the superposition and convolution
approaches are used simultaneously. The superposition principle also can be used to super-
impose the drawdown on the natural (ambient) flow conditions. Using this principle leads to
h(x, y, t) H(x, y, t) s(x, y, t) (4.47)
where h transient potentiometric surface that combines ambient conditions and well
impact, H potentiometric surface under natural (ambient) conditions, and s transient
drawdown.
4.3.3 Interception Wells
With respect to contaminant transport in the subsurface, interception wells are used to trap
the contaminant plume within the well flow field. It is assumed in this analysis that there
is an ambient steady-state uniform flow through the aquifer. The combination of well-
related flow and ambient uniform flow satisfies the conditions of two-dimensional poten-
tial flow in a horizontal plane, where the discharge described by stream function y is relat-
ed to potential , or the piezometric head h. The extent of the aquifer through which water
travels to the well and is captured by it is called the capture zone. The derivation of the
analytical solution for steady-state flow capture-zone uses the following assumptions:
(1) ahomogeneous, isotropic, infinitely large aquifer, (2) uniform flow, (3) no leakage, (4)
aquifer storativity or specific yield neglected, (not relevant for steady-state analysis),
(5) hydrodynamic dispersion neglected, (6) the Dupuit assumption applies, and (7) the
well is fully penetrating and pumping at a constant rate. Three important parameters are
used in delineating the capture zone: namely, the stagnation point, the upgradient maxi-
mum width of the capture zone, and the equation for the capture zone boundary.
For a confined aquifer, the distance from the well to the stagnation point (measured in
the direction of the uniform flow) is
x
STAG
2
Q
T
w
I
(4.48)
where Q
w
well discharge, T aquifer transmissivity KB (K aquifer permeability,
B aquifer depth), and I natural hydraulic gradient: i.e., the gradient responsible for
the ambient steady-state uniform flow in the aquifer. The upgradient divide, defined by
the maximum width of the capture zone far upgradient of the well, for the confined aquifer
is given by
w
DIV
Q
TI
w
(4.49)
and the equation of the dividing streamline is
x (4.50)
The procedure for delineating the capture zone consists of the following steps: (1) esti-
mate the location of the stagnation point (x
STAG
, 0), (2) estimate the maximum width of the
capture zone w
DIV
, and (3) vary y between zero and w
DIV
/2 and use the capture zone bound-
ary to estimate the boundary location (x,y).
4.3.4 Partially Penetrating Wells
Performance of wells that penetrate only partially through the bearing strata is discussed
in this section. The simplest case consists of a well that is barely penetrating into an semi-
y
tan
2
Q
T
w
Iy
4.10 Chapter Four

infinite porous medium so that the aquifer flow is three-dimensional and spherically sym-
metric. In this case, the following relationship applies between the flow into the partially
penetrating well Q
p
and the flow to a fully penetrating one Q:
Q
Q
p
r
B
w
ln
r
R
w
(4.51)
where B is the aquifer thickness, r
w
is the well radius, and R is the radius of influence of
the partially penetrating well. Because, in general, r
w
B, then the equation above indi-
cates that the spherical flow to a partially penetrating well is highly inefficient compared
with simple radial flow: i.e., for the same drawdown in the well, it results in a significantly
smaller pumping rate.
In the general case of partial penetration, one may consider the total drawdown s
T
,
which consists of the drawdown equivalent to that of a fully penetrating well s and addi-
tional head loss because of the partial penetration of the well s:
s
T
s s (4.51)
Additional head loss for a well penetrating from the top (or the bottom) of the aquifer
is estimated as follows:
s
Q(
2
1
Tp
p)
ln

(1
r
w
p)h
s
1
1
]
(4.53)
where p penetration factor; p h
s
/B; h
s
penetration depth; and B aquifer
thickness (Fig. 4.2). For the well centrally positioned in the aquifer, the following formu-
la is used:
s
Q(
2
1
Tp
p)
ln

(1
2r
w
p)h
s
1
1
]
(4.54)
Thus, when the pumping rate is defined for a well, we calculate the drawdown correc-
tion s and add it to the full penetration drawdown s. However, when the drawdown is
given for a well, we have to recalculate the pumping rate. In this case, the true pumping
FIGURE 4.2 Partially-penetrating well.
B
h
s
h
s
B/2
h
s
/2
2r
w
rate is given by
Q
s
Q
s
s
s
S
T
S
T
s
(4.55)
where s drawdown defined at the well, Q pumping rate estimated using s, and
Q
p
actual pumping rate
4.3.5 Well Duplets
Well duplets, each of which consists of one pumping and one recharge well, are frequent-
ly used as a means of injecting and removing aquifer mitigation solutes, such as co-sol-
vents, surfactants, or both. Typically, the recharge well is positioned directly upgradient
from the discharge well, and the magnitudes of pumping and injection rates are the same.
In this case, the two wells form a flow circulation cell: i.e., all the injected water is
pumped out by the discharge well. In the case of co-solvent flushing, it is important to
understand what region of the aquifer is subject to the mitigation: i.e., what the boundary
is of the circulation cell. This boundary is defined by the upgradient and downgradient
stagnation points (x
STAG
, 0) and (x
STAG
, 0) and the cell boundary equation. For the x-axis
parallel to the direction of ambient flow and the origin of the coordinate system located at
the mid-point between the two wells, the two stagnation points, (x
STAG
, 0) and (x
STAG
, 0)
are given as the roots of the quadratic equation
q
Q
o
B
w
d
2
1
(x/d
x
/d
1)
2
(x/d
x/
d
1)
2
_
,
0 (4.56)
where q
o
ambient flux, 2d distance between the wells, and Q
w
pumping/injection
rate. The boundary of the circulation cell is defined by
q
Q
o
B
w
y
2
1
tan
1
(x/d
y/
d
1)
1
1
]
tan
1

(x/d
y/
d
1)
1
1
]
_
1
2
(4.57)
The circulation cell is symmetric with respect to the y axis. The cell delineation pro-
cedure consists of estimating the locations of the stagnation points and varying x between
zero and x
STAG
and using the cell-boundary equation to solve for y. This implicit equation
can be solved by any calculation software, such as Mathematica or MS Excel.
4.3.6 Transport Equations
The following general form of mass transport equation in the saturated zone is derived assum-
ing one-dimensional advective and three-dimensional diffusive-dispersive transport in the
aqueous phase, linear partitioning of a compound between the three phases (water-soil-
(D)NAPL), and first-order degradation in the aqueous phase. For this conditions, we have
R
x
i

i
v
C
x
W
i
C
x
1
W
C
W
(4.58)
where C
W
aqueous phase concentration, v pore-water velocity, and
W
volumetric
moisture content, and
i
longitudinal, transverse horizontal, and transverse vertical
D
W
C
W
4.12 Chapter Four

macrodispersivities, and D Millington-Quirk dispersion coefficient, and first-order
degradation rate in the aqueous phase, and R retardation factor,
R 1
k
S
OI
W
L
k
NAP
W
NAPL
(4.59)
where k
SOIL
water-soil partitioning coefficient, k
SOIL
S/C
W
, S weight/weight con-
centration of absorbed compound in soil, k
NAPL
NAPL water partitioning coefficient,
k
NAPL
C
NAPL/
C
W
, C
NAPL
concentration of compound in the NAPL phase,
B
bulk den-
sity of dry soil, and
NAPL
volumetric NAPL content.
Assuming that the diffusive fluxes are negligible compared the macrodispersive flux-
es, the transport equation can be simplified to yield
t
W
x
i
i
v
R
C
x
W
i
,
v
R

R
C
W
(4.60)
where v
R
v/R and
R
/
R
.
4.3.7 Selected Analytical Solutions
Closed-form solutions are available for a variety of flow, boundary, and initial conditions.
Van Genuchten and Alves (1982) presented a good summary of these solutions. Some of
the most useful solutions are presented below.
4.3.7.1 One-dimensional transport with step change in concentrationno degrada-
tion. This simple case has the initial condition C(x,0) 0 for x 0, and it is subject to
the following boundary conditions: C(0,t) C
o
, t 0 and C(,t) 0, t 0. The solution
of the transport equation for these conditions is given by
C(x,t)
C
2
O

Erfc

2(
x
x
v
R
v
t
R
)
t
1/2
1
1
]
exp
x
x
1
1
]
Erfc

2(
x
x
v
R
v
t
R
)
t
1/2
1
1
]
(4.61)
4.3.7.2 One-dimensional transport with step change in concentration and first-order
degradation. The initial and boundary conditions are the same as in Sec. 4.7.1.
The solution is given by
C(x,t)
C
2
O
exp
2
x
1
_
,
1/2
_
,
1
1
]
Erfc

(4.62)
where Erfc complementary error function.
4.3.7.3 Continuous point injection, 2-D dispersive transport, no retardation, and no
degradation. A tracer is continuously injected at a rate Q (per unit depth of the aquifer)
x v
R
4
v
R
R
1/2
t
2(
x
v
R
t)
1/2
4
R
v
R
C
W
x
i
with a concentration C
o
into a uniform flow field from a point (x 0, y 0). Let the
uniform velocity be v
x
. The asymtotic solution, i.e., for t , is given by
C(x,y)
,
exp
2D
v
x
L
x
D
T
,
K
o
D
x
2
L
D
y
2
T
1
1
]
(4.63)
where K
o
modified Bessel function of the second kind and of 0th order (Bear, 1972).
The time-dependent solution is
C(x,y)
,
exp
2
v
D
x
x
L
,
K
o
[W(0,)] W(t,) (4.64)
where

4
v
D
x
2
D
x
2
L
(4.65)
W (t, b) leaky well function (see, for example, Hunt, 1983, p. 100).
4.3.7.4 Point slug injection into a uniform flow field3-D transport and retardation.
In this case, a slug of contaminant of the mass MC
o
V is injected at point (0,0,0). The
transient distribution of concentration is described by
C(x, y, z, t)
8(v
R
t)
3
V
/2
o
(
C
o
x
z
)
1/2
exp
(x
4
x
v
v
R
R
t
t)
2
4
y
y
2
v
R
t
4
z
z
2
v
R
t
1
1
]
(4.66)
4.3.7.5 Continuous injection from a finite-sized source with retardation and degrada-
tion. In this case, consider transport from a rectangular source that is perpendicular
to the direction of flow. The source width is Y, and its depth below the water table is Z.
The transient concentration distribution in the presence of retardation and degradation is
given by
C(x, y, z, t)
C
8
o

exp
2
x
1
v
4
R
R
x
,
1/2
1
1
]
Erfc

1
1
]
Erfc

2
y
(
y
x
Y
)
/
1
2
/2
1
1
]
Erfc
2
y
(
y
x
Y
)
/
1
2
/2
1
1
]
Erfc

2
z
(
z
x)
Z
1/2
1
1
]
Erfc

2
z
(
z
x)
Z
1/2
1
1
]
(4.67)
x v
R
t(1 4
R
v
x
)
1/2
2(
x
v
R
t)
1/2
y
2
D
T
C
o
Q
2D
L
D
T
v
x
2
4D
L
C
o
2D
L
D
r
4.14 Chapter Four
4.4 FLOW AND TRANSPORT IN UNSATURATED
ZONE AQUEOUS PHASE
In this section, we briefly discuss the flow continuity equations and present some simple
solutions to selected flow problems. That discussion is followed by a presentation of mass
transport in the water phase of unsaturated zone.
4.4.1 Flow in an Unsaturated Zone
The continuity equation for an unsaturated flow system can be written as
.q (4.68)
or
q
x
x
q
y
y
q
z
z
,
(4.69)
Combining Darcy's law with the mass continuity equation, we can write the final flow
equations is
(K()h) (4.70)
The flow equations can be simplified for horizontal and vertical flow conditions.
a. One-dimensional horizontal flow:
K()
,
(4.71)
where volumetric water content. In this, the contribution of the elevation head, z,
vanishes, since z/x 0.
b. One-dimensional vertical flow:
K()
1
_
,
_
,
(4.72)
Note that the flow equations are characterized by the presence of two dependent, albeit
related, variables: namely, and . To simplify this situation, we describe the relation-
ship between and by a term called soil diffusivity D() as
D()
K
C
(
(
)
)
(4.73)
where C() is called specific moisture capacity and is defined as
C()
(4.74)
Using these definitions, the flow equation can be written as follows:
c. One-dimensional horizontal flow:
D
x
()
,
(4.75)
d. One-dimensional 1-D vertical flow:
(D
z
()
K
z
()) (4.76)
As can be seen, we now have only one dependent variable: namely, . The only limitation of
this formulation is that specific moisture capacity C() becomes zero in the capillary fringe
zone, thus making the solution impossible. Therefore, this formulation is valid only in the par-
tially saturated zone (water content less than saturated value), not in the capillary fringe.
Another way to solve this problem, which does not have the limitation discussed
above, is to formulate the flow equations in terms of soil suction . For the vertical flow,
we obtain
C()
K
z
()(
1)
(4.74)
Exercise. Consider steady-state vertical infiltration from the soil surface to the water table
at depth L. The relative hydraulic conductivity of the soil is described by the following
exponential law:
k
r
() exp[ ] (4.78)
Derive an expression for the vertical distribution of h. After the first integration of the
flow equation, we obtain
K
z
()
1
_
,
q (4.79)
where q infiltration rate and K is a function of capillary pressure y.
K
z
() K
sat
exp[] (4.80)
where h z . Substitution of these relationships into the flow equation leads to
exp
(h z)
1
1
]
h
z
K
q
SAT
(4.81)
or
exp[h]dh
K
q
SAT
exp[x]dx (4.82)
After the second integration, we obtain
exp[h]
K
q
SAT

exp[z] C
1
(4.83)
Substituting the boundary condition h(0) 0 and solving for C
1
yields the following
expression for the total head h:
h(z)
1

ln

K
q
SAT
(exp[z] 1) 1
1
1
]
(4.84)
4.4.2 Transport in an Unsaturated Zone
The mass continuity equation for an unsaturated flow system with advection and diffu-
sion/dispersion in the aquoeus phase, diffusion in the vapor phase, partitioning between
four phases (soil, water, vapor, and (D)NAPL), and first-order degradation in the aqueous
phase can be written as
4.16 Chapter Four
R
C
t
W
x
i
i
v
D
W
v
k
W
AIR
C
x
W
i
,
v
C
x
1
W
C
W
(4.85)
where C
W
aqueous phase concentration; v pore-water velocity;
W
volumetric
moisture content;
i
longitudinal, transverse horizontal, and transverse vertical
macrodispersivities; D Millington-Quirk dispersion coefficient; D
v
Millington-Quirk
dispersion coefficient in the vapor phase; first-order degradation rate in the aquoeus
phase; and R retardation factor;
R 1
k
S
OI
W
L
k
NAP
W
NAPL
k
AI
W
AIR
(4.86)
where k
SOIL
SOIL
S/C
W
NAPL
NAPL-water partitioning coefficient,
k
NAPL
C
NAPL
/C
W
, C
NAPL
concentration of compound in the NAPL phase, k
AIR
vapor-
water partitioning coefficient, k
AIR
V/C
W
, V concentration of compound in the vapor
phase,
B
bulk density of dry soil,
AIR
volumetric vapor content, and
NAPL
volu-
metric NAPL content.
Assuming again that the diffusive fluxes are negligible compared with the macrodis-
persive and advective fluxes, the transport equation can be simplified to yield
C
t
W
x
i

i
v
R
C
x
W
i
,
v
R
C
x
W
i
R
C
W
(4.87)
where v
R
v/R and
R
/R. Note that the form of this equation is the same as the form
of the one for transport in the saturated zone; therefore, the analytical solutions presented
for the saturated transport are valid for the unsaturated conditions. This is particularly true
for the one-dimensional (vertical) transport equations, which are of primary interest in the
case of unsaturated fate and transport of compounds.
4.5 FLOW AND TRANSPORT IN VAPOR PHASE
This section, presents the soil vapor flow equations. This is followed by selected solutions
to vapor flow problems. Finally, we discuss diffusive transport in the vapor phase.
4.5.1 Soil Vapor Flow
The flow of gases in a porous medium can be described by combining the following
equations:
a. The equation of continuity is
(v) n
(4.88)
with vapor density, v Darcys flux vector,
AIR
air-filled porosity, and t time.
b. The perfect gas law is

m
v
p
R
M
T
(4.89)
with m gas mass, V gas volume, p absolute pressure, Mmolar mass, T
absolute temperature K, and R universal gas constant.
c. Darcys law for vapor flow is
v
p (4.90)
where k soil intrinsic permeability and gas viscosity. The resulting governing
equation is 1953
2
p
2
2n
k
p
t
(4.91)
(Bruce et al., 1953).
d. The molar flux [moles/unit area-time] is given by
q
R
k
T

pp (4.92)
For one-dimensional flow, the governing equation reduces to
2
x
p
2
2
2
A
k
IR
p
t
(4.93)
and for radial flow, the governing equation is
2
r
p
2
2
1
r

p
r
2

2
A
k
IR
p
t
. (4.94)
For steady state, exact analytical solutions for gas flow are obtained by using the fol-
lowing transformation (Cho, 1991):
m
K ( p
2
2
p
r
2
)
(4.95)
where m is referred to as the discharge potential. The governing equation now becomes
Laplace's equation:
2
m 0 (4.96)
For example, the exact solution for the point source in three-dimensional space is given by
m
4
Q
r
(4.97)
where Q source strength and r distance from source point.
To estimate the time required to achieve steady-state vapor flow, Johnson et al. (1990)
presented a method based on the solution of radial flow of vapor to a well. Their results
are summarized in Fig. 2 of Johnson et al. (1990 b) for values of k corresponding to sandy
soil. They also presented a method to estimate vapor flow rates, pressure distributions, and
vapor velocities in unsaturated soils based on the steady-state solution to the governing
equation of vapor radial flow: namely,
2
p
2
2n
k
p
t
(4.98)
The pressure p can be expressed in terms of the ambient pressure p
Atm
and a deviation
p from this pressure: p is equivalent to the vacuum that would be measured in the soil. If
this substitution is used in the flow equation and if we neglect the product p'
2
relative to
the product p
Atm
p (linearization), then the resulting equation for radial flow is
4.18 Chapter Four
p
A
A
IR
T
p
t
1
r

p
r
,
(4.99)
The solution to this equation for the following boundary conditions is
p 0, for r
lim
r0
p
r
2B
Q
k/
(4.100)
as given by
p
4B
Q
(k/)

exp[ x]dx
4B
Q
(k/)

W(u) (4.101)
where Q is the volumetric flow rate to the vapor well. The well function W(u) is tabulat-
ed in almost all groundwater textbooks. The behavior of the integral is such that for
(r
2
AIR
/4kp
Atm
t) 0.001, its value is close to the asymptotic steady-state limit.
Exercise. Given the following parametershydraulic conductivity K 102 cm/sec,
air viscosity
AIR
0.018 cp, volumetric air content (equal to porosity)
AIR
0.3, and
local pressure gradient dp/dx 0.01 atm/cmestimate the pore-vapor velocity. From the
conversion table (Domenico and Schwartz, 1990), we have
k[darcy] K[m/s]*1.04*10
5
(4.102)
Thus, k 10.4 darcy. The vapor flux is given by
q
i

k
r
(
f
)
lu
k
id
fluid
x
p
i
x
z
i
,
(4.103)
Assuming that k
r
1.0, we obtain
q[cm/sec]
k
[
r
c
*
e
k
n
[
t
d
i
a
p
r
o
c
is
y
e
]
]
p
x
a
c
t
m
m
1
1
]

10.
0
4
.
*
01
0
8
.01
5.78[cm/sec] (4.104)
Finally, we estimate the pore-vapor velocity v q/
AIR
19.26 cm/s.
4.5.2 Transport in Vapor Phase
It is usual to assume that whenever advective vapor flow is present, it dominates the trans-
port process and the diffusive/dispersive processes can be neglected. In this case, the fate
and transport equation for a compound that partitions between the four phases (soil, water,
vapor, and (DNAPL) and is subject to first-order degradation in the aqueous phase is
R
V
t
v
AIR
x
V
1
A
W
IR
k
AW
V (4.105)
where: V vapor phase concentration, v
AIR
pore-air velocity,
W
volumetric mois-
ture content,
AIR
volumetric vapor content, first-order degradation rate in the
aqueous phase, k
A W
air-water partitioning coefficient, k
AW
C
W
/V, and R retar-
dation factor,
u
r
4
2
k
p
A
A
IR
T

R 1
k
A
W
A
k
I
S
R
OIL
k
A W
k
N
A
A
IR
PL
NAPL
k
A
A
W
IR
(4.106)
where: k
SOIL
SOIL
S/C
W
NAPL
NAPL-water partitioning coefficient,
k
NAPL
C
NAPL
/C
W
, C
NAPL
concentration of compound in the NAPL phase, k
AIR
vapor-
water partitioning coefficient, k
AIR
V/C
W
, V concentration of compound in the vapor
phase,
B
bulk density of dry soil,
AIR
volumetric vapor content, and
NAPL
volu-
metric NAPL content.
Division of the transport equation by the retardation factor yields
V
t
v
AIR,R
x
V
1
*
R
V (4.107)
where v
Air,R
v
AIR
/R and R k
A W
W
/(
AIR
R). Note that the form of this equation is the
same as the form of the one for transport in the saturated zone, except for the absence of
the dispersive term. Therefore, the analytical solutions presented for the saturated trans-
port are valid for the vapor transport conditions.
When there is no advective transport in the vapor phase, the transport equation must
include diffusive fluxes in vapor and aqueous phases to yield
R
V
t
x
i
D
v
V
x
i
Dk
A W
V
x
i
A
W
IR
k
A W
V (4.108)
where D Millington-Quirk dispersion coefficient for the aqueous phase, and D
v
Millington-Quirk dispersion coefficient in the vapor phase. Assuming that the dispersion
coefficients do not vary in space leads to the following form of the transport equation:
V
t
2
x
V
i
2
V (4.109)
where
D
D
v
D
R
k
A W
(4.110)
and
I
W
R
R
(4.111)
Again, we note the similarity of this fate and transport equation to the one presented
for saturated transport and conclude that all the analytical solutions presented in Sec. 4.2
can, in principle, be used to analyze vapor phase transport.
Exercise. Given that water saturation S
w
0.20, porosity n 0.4, compound concentra-
tion in soil vapor at depth L 2 m C
o
100 mg/L, compound concentration at the soil
surface C
s
0.01, and molecular diffusion coefficient of the compound D
o
0.087cm2/sec, estimate the compound mass flux in the vapor phase at the soil surface. The
effective vapor-phase diffusion coefficient is given by
D D
o
n
A
3
2
.33
0.0026 cm
3
/s (4.20)
and the mass flux of compound A is estimated as follows:
4.20 Chapter Four
q D
C
x
Co
L
Cs
0.0026[cm
2
/s]
100*
2
1
0
0
0
3
[
[
c
m
m
g
]
/cm
3
]
1.3[mg/(cm
2
s)] (4.112)
Exercise. Consider advective transport of a compound in vapor phase. The compound
partitions between vapor and aqueous phases according to the relationship
V K C (4.113)
where V concentration in vapor phase, C concentration in aqueous phase, and K
partitioning coefficient. Given vapor flux q, porosity n, and water saturation S
w
, estimate
the apparent (retarded) velocity of the compound. From the advective transport equation,
we have
C
t
T
V
x
(4.114)
where
C
T
C S
W
n V(1 S
W
)n Vn (1 S
W
)
K(1
S
W
S
W
1
_
,
(4.115)
Thus, for nonretarded tracers, we have

V
V
x
(4.116)
where pore-vapor velocity is
v
n(1
q
S
w
)
(4.117)
whereas for retarded compounds, we have
V
t
v
R
V
x
(4.118)
where the retarded velocity is given by
v
R
R
v
1 (4.119)
Exercise. Consider diffusive vertical transport of a compound in vapor phase. The com-
pound is subject to first-order degradation in the aqueous phase at rate and to partitions
between vapor and aqueous phases according to the following relationship:
V K C (4.113)
where V concentration in vapor phase, C concentration in aqueous phase, and K
partitioning coefficient. At the depth of 100 cm below the ground surface, the vapor con-
centration of the compound was measured to be V
o
, whereas at the ground surface the con-
centration was V
s
. Given the compounds diffusion coefficient in vapor phase D
o
, porosi-
ty n, and water saturation S
w
, estimate the diffusive flux of the compound at the soil sur-
face. The relevant mass transport equation is given by
v
K(1
S
W
S
W
)

D
2
x
V
2
nS
w
C 0 (4.120)
where
D D
o
n
A
3.
2
33
(4.19)
Substituting C V/K into the mass transport equation leads to
2
x
V
2
*
2
V 0 (4.121)
where
*
2
K
n
D
S
w
(4.122)
We solve the modified mass transport equation to obtain
V(x) C
1
exp[
x] C
2
exp[
x] (4.123)
where constants C
1
and C
2
are obtained from the boundary conditions
V(0) V
o
, and V(100) V
s
(4.124)
The compound's mass flux at the soil surface is estimated from
q D
(
x
x)

@x 100 (4.125)
REFERENCES
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