Lecture 3

Contaminant Transport
Mechanisms and Principles
BASIC DEFINITIONS
Ground surface
Below
ground
surface
(BGS)
Vadose zone,
unsaturated zone
Capillary fringe
Water table
Saturated zone
Confining bed
Confined aquifer or
artesian aquifer
Water-table, phreatic,
or unconfined aquifer
Capillary fringe may be >200 cm in fine silt
In capillary fringe water is nearly saturated, but held in tension in soil pores
MICRO VIEW OF UNSATURATED ZONE
air
water
solid
Contaminant concentrations:
C
w
, mg/L
concentration in water
C
g
, mg/L or ppmv
concentration in gas
C
s
, gm/kg
concentration in solids
PARTITIONING RELATIONSHIPS
Solid water
K
d
= partition coefficient
Water vapor
H = Henrys Law constant
water mg/L
solid mg/kg
K
C
C
d
w
s
= =
water mg/m
air mol/m
H
C
C
3
3
w
g
= =
HENRYS LAW CONSTANT
H has dimensions: atm m
3
/ mol
H is dimensionless
H = H/RT
R = gas constant = 8.20575 x 10
-5
atm m
3
/mol K
T = temperature in K
NOTE ON SOIL GAS CONCENTRATION
Soil gas is usually reported as:
ppmv = parts per million by volume
g/mole weight molecular
mL/mole 24,000 (mg/L) C
(ppmv) C
g
g

=
VOLUME REPRESENTATION
Gas volume, V
g
Water volume, V
W
Solid volume, V
S
Total volume, V
T
Void volume, V
V
VOLUME-RELATED PROPERTIES
Bulk density =
b
= mass of solids
total volume
Porosity = n = = V
V
/V
T
Volumetric water content or
water-filled porosity =
W
= V
W
/V
T
Saturation = S = V
W
/V
V
Gas-filled porosity =
g
(or
a
) = V
g
/V
T

W
+
g
= n
CONTAMINANT CONCENTRATION
IN SOIL
Total mass in unit volume of soil:
C
T
=
b
C
s
+
w
C
W
+
g
C
g
If soil is saturated,
g
= 0 and
W
= n
C
T
=
b
C
s
+ n C
W
NOMENCLATURE FOR DARCYS LAW
Q = K i A
K = hydraulic conductivity
i = hydraulic gradient = dh/dL
A = cross-sectional area
Velocity of ground-water movement
u = Q / n A = q / n = K i / n = average linear velocity
n A = area through which ground water flows
q = Q / A = Darcy seepage velocity = Specific discharge
For transport, n is n
e
, effective porosity
ADVECTIVE FLUX
Flowing ground water carries any dissolved
material with it Advective Flux
J
A
= n u C mass / area / time
= mass flux through unit cross section due to
ground-water advection
n is needed since no flow except in pores
DIFFUSIVE FLUX
Movement of mass by molecular diffusion (Brownian
motion) proportional to concentration gradient
in surface water !!!
D
O
is molecular diffusion coefficient [L
2
/T]
x
C
D J
O D

=
DIFFUSIVE FLUX
In porous medium, geometry imposes constraints:
= tortuosity factor
D* = effective diffusion coefficient
Factor n must be included since diffusion is only in pores
x
C
n * D
x
C
n D J
O D

=
TORTUOSITY
Solute must travel a tortuous path, winding through
pores and around solid grains
Common empirical expression:
L = straight-line distance
L
e
= actual (effective) path
0.7 for sand
2
e
L
L

=
NOTES ON DIFFUSION
Diffusion is not a big factor in saturated ground-
water flow dispersion dominates diffusion
Diffusion can be important (even dominant) in
vapor transport in unsaturated zone
MECHANICAL DISPERSION
A
B
C
A
B
C
A arrives first, then B, then C mechanical dispersion
MECHANICAL DISPERSION
Viewed at micro-scale (i.e., pore scale) arrival
times A, B, and C can be predicted
Averaging travel paths A, B, and C leads to
apparent spreading of contaminant about the
mean
Spatial averaging dispersion
MECHANICAL DISPERSION
Dispersion can be effectively approximated by the
same relationship as diffusioni.e., that flux is
proportional to concentration gradient:
Dispersion coefficient, D
M
=
L
u

L
= longitudinal dispersivity (units of length)
x
C
n D J
M M

=
TRADITIONAL VIEW OF
HYDRODYNAMIC DISPERSION
ACTUAL OBSERVATIONS OF PLUMES
USGS Cape Cod
Research Site
Source: NOAA Coastal Services Center,
http://www.csc.noaa.gov/crs/tcm/98fall_status.html
Accessed May 14, 2004.
Source: U.S. Geological Survey, Cape Cod Toxic
Substances Hydrology Research Site,
http://ma.water.usgs.gov/CapeCodToxics/location.html.
Accessed May 14, 2004.
MONITORING WELL
ARRAY
USGS MONITORING NETWORK
Source: http://ma.water.usgs.gov/CapeCodToxics/photo-gallery.html Photo by D.R. LeBlanc.
OBSERVED
BROMIDE PLUME
HORIZONTAL
VIEW
Significant longitudinal
dispersion, but limited
lateral dispersion
OBSERVED BROMIDE PLUME
VERTICAL VIEW
Limited vertical dispersion
LONGITUDINAL
DISPERSION VS. LENGTH SCALE
Lateral and vertical dispersivity
TRANSPORT EQUATION
Combined transport from advection, diffusion, and
dispersion (in one dimension):
D
H
= D* + D
M
= D
O
+
L
u
= hydrodynamic dispersion
x
C
D nuC J
x
C
n D
x
C
n * D nuC J
J J J J
H
M
M D A

=
+ + =
TRANSPORT EQUATION
Consider conservation of mass over control
volume (REV) of aquifer.
REV = Representative Elementary Volume
REV must contain enough pores to get a
meaningful representation (statistical average
or model)
TRANSPORT EQUATION
S / S
x
J
t
C
S / S J
t
C
T
T

Change in
contaminant
mass with
time
Flux in less
flux out of
REV
Sources and
sinks due to
reactions
(1)
(2)
TRANSPORT EQUATION
C
T
= total mass (dissolved mass plus mass adsorbed to
solid) per unit volume
=
b
C
S
+ n C
W
=
b
C
S
+ n C (3)
Substitute Equation 3 into Equation 2:
( ) ( )
S / S
x
C
n D nuC
x t
nC
t
C
H
S b

(4)
no solid phase in flux term
Note: W subscript dropped for convenience and for
Consistency with conventional notation
TRANSPORT EQUATION
2
2
d b
H
d b
2
2
H d b
x
C
n
n K
D
x
C
n
n K
u
t
C
x
C
nD
x
C
nu
t
C
n K

+
+

+
=

+
(5)
C
S
= K
d
C by definition of K
d
Assume spatially uniform n,
b
, K
d
, u, and D
H
and no S/S
(6)
TRANSPORT EQUATION
d
d b d b
R
n
K
1
n
n K
=

+ =
+
Retardation factor, R
d
2
2
d
H
d
x
C
R
D
x
C
R
u
t
C

Substituting Equation 7 into Equation 6:

(8)
(7)
Effect of adsorption to solids is an apparent slowing of transport
of dissolved contaminants
Both u and D
H
are slowed
SOLUTION OF TRANSPORT EQUATION
Equation 8 can be solved with a variety of
boundary conditions
In general, equation predicts a spreading
Gaussian cloud
[[
0.0
t
1
t
2
t
0
0.2
0.4
0.6
0.8
1.0
x - a
x
-
x + a
Spreading of a solute slug with time due to diffusion. A slug of solute was
injected into the aquifer at time t with a resulting initial concentration of C .
0
0
Adapted from: Fetter, C. W. Contaminant Hydrogeology.
New York: Macmillan Publishing Company, 1992.
C
/
C
0
R
e
l
a
t
i
v
e

C
o
n
c
e
n
t
r
a
t
i
o
n
1-D SOLUTION OF TRANSPORT EQUATION
For instantaneous placement of a long-lasting source
(for example, a spill that leaves a residual in the soil),
solution is:
Where C
o
= C(x=0, t) = constant concentration at
source location x = 0
Solution is a front moving with velocity u/R
d
( )

=
t D R 4
ut x R
erfc
2
C
t , x C
H d
d o
+
0.0
0.2
0.3
0.1
0.16
0.50
0.84
0.4
0.6
0.7
0.8
0.9
1.0
M
e
a
n
s s
x =
x
ut/R
d
Adapted from Fetter, C. W. Contaminant Hydrogeology.
New York: Macmillan Publishing Company, 1992.
C
/
C
0
R
e
l
a
t
i
v
e

C
o
n
c
e
n
t
r
a
t
i
o
n
The profile of a diffusing front as predicted by the complementary error function.
Moving front of contaminant from constant source
Moving front of contaminant from constant source
0
1
2
3
4
5
6
7
8
9
10
0 1 2 3 4 5 6 7 8 9
Distance, x
C
o
n
c
e
n
t
r
a
t
i
o
n
,

C
(
x
,
t
)
C
0
= 10
u = 1
D
H
= 0.1
R
d
= 1
t = 1
ut = 1
t = 5
ut = 5
t = 3
ut = 3
Effect of dispersion coefficient
Effect of retardation
Effect of R
d
on moving front of contaminant
0
1
2
3
4
5
6
7
8
9
10
0 1 2 3 4 5 6 7 8 9
Distance, x
C
o
n
c
e
n
t
r
a
t
i
o
n
,

C
(
x
,
t
)
C
0
= 10
u = 1
D
H
= 0.1
t = 3
ut = 3
R
d
= 2
t = 3
ut = 3
R
d
= 1
1-D SOLUTIONS
Mass
input here
Front at
time t
1-D
M
C
=
M
L
2
M
M
L
2
T
M
exp-
2n D
t = 0
t = t
1
1/2 1/2
x = 0
v
to
x = 0 x = 0
v
v
p
x
x t
[ [
(x-vt)
4D t
2
C=
M
erfc
2nv
D
x
( (
x-vt
t
C =
M
nv
for x > 0

( (
M, M are instantaneous
or continuous plane
sources
.
.
.
.
2
Transport of a Conservative Substance from Pulse and Continuous Sources
Dimensions Pulse Input of Mass M
Continuous Input of Mass Per
Unit Time M Starting at Time t = 0
.
Continuous Input of Mass Per
Unit Time M in Steady State
.
Adapted from: Hemond, H. F. and E. J. Fechner-Levy. Chemical Fate and Transport in the Environment.
2nd ed. San Diego: Academic Press, 2000.
Mass
input here
2-D SOLUTIONS
2-D
M, M are instantaneous
or continuous line
sources
M
M
L
[ [
M
M
L-T
[ [
t = 0 t = t
Plume at time t
1
to
v
v
v
x
x
y y

.
.
x
y
C=
M
exp
4n D
p
x
x D
y
y [ [
(x-vt)
4D t
t
2
y
4D t
2
+ C=
M
exp erfc
4n (vr)
1/2 1/2
p x
D
y
D t
x
[ [
(x-r)v
2D ( (
r-vt
2
Transport of a Conservative Substance from Pulse and Continuous Sources
Adapted from: Hemond, H. F. and E. J. Fechner-Levy. Chemical Fate and Transport in the Environment.
2nd ed. San Diego: Academic Press, 2000.
Dimensions Pulse Input of Mass M
Continuous Input of Mass Per
Unit Time M Starting at Time t = 0
Continuous Input of Mass Per
Unit Time M in Steady State
.
.
C=
M
exp
2n (vr)
1/2 1/2
p x
D
y
[ [
(x-r)v
2D
.
.
3-D SOLUTIONS
3-D
M, M are instantaneous
or continuous point
sources
M
M
L
[ [
M
M
T
[ [
v
v
.
.
C=
M
exp erfc
8n r p x
D
y
D t
x
[ [
(x-r)v
2D ( (
r-vt
2
Transport of a Conservative Substance from Pulse and Continuous Sources
Adapted from: Hemond, H. F. and E. J. Fechner-Levy. Chemical Fate and Transport in the Environment.
2nd ed. San Diego: Academic Press, 2000.
Dimensions Pulse Input of Mass M
Continuous Input of Mass Per
Unit Time M Starting at Time t = 0
Continuous Input of Mass Per
Unit Time M in Steady State
.
.
C=
M
exp
x
[ [
(x-r)v
2D
.
.
v
C
=
M
exp-
8n D
t = 0
t = t
1
3/2 3/2
to
p
x
D
y
x
t
[ [
(x-vt)
4D t
2
2
y
y
2
z
4D t

D
z
D
z
4n r p
D
y
D
z
+ +
z
4D t
z
y
x
z
y
Plume at time t
z
y