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Lecture 3

Contaminant Transport
Mechanisms and Principles
BASIC DEFINITIONS

Ground surface

Vadose zone, Below


unsaturated zone
ground
surface
(BGS)
Capillary fringe
Water table Water-table, phreatic,
Saturated zone or unconfined aquifer
Confining bed
Confined aquifer or
artesian 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

Contaminant concentrations:

water Cw, mg/L


concentration in water
air
Cg, mg/L or ppmv
concentration in gas
solid
Cs, gm/kg
concentration in solids
PARTITIONING RELATIONSHIPS

Cs mg/kg solid
Solid ↔ water = Kd =
Cw mg/L water
Kd = partition coefficient

Water ↔ vapor Cg mol/m3 air


=H= 3
Cw mg/m water
H = Henry’s Law constant
HENRY’S LAW CONSTANT

H has dimensions: atm m3 / mol

H’ is dimensionless

H’ = H/RT
R = gas constant = 8.20575 x 10-5 atm m3/mol °K
T = temperature in °K
NOTE ON SOIL GAS CONCENTRATION

Soil gas is usually reported as:


ppmv = parts per million by volume

Cg (mg/L) × 24,000 mL/mole


Cg (ppmv) =
molecular weight g/mole
VOLUME REPRESENTATION

Gas volume, Vg

Void volume, VV
Water volume, VW
Total volume, VT

Solid volume, VS
VOLUME-RELATED PROPERTIES
Bulk density = ρb = mass of solids
total volume
Porosity = n = θ = VV/VT
Volumetric water content or
water-filled porosity = θW = VW/VT
Saturation = S = VW/VV
Gas-filled porosity = θg (or θa) = Vg/VT

θW + θg = n
CONTAMINANT CONCENTRATION
IN SOIL

Total mass in unit volume of soil:


CT = ρb Cs + θw CW + θg Cg

If soil is saturated, θg = 0 and θW = n


CT = ρb Cs + n CW
NOMENCLATURE FOR DARCY’S LAW

Q = KiA
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 ne, effective porosity
ADVECTIVE FLUX

Flowing ground water carries any dissolved


material with it → Advective Flux

JA = 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
∂C
JD = −DO in surface water !!!
∂x
DO is molecular diffusion coefficient [L2/T]
DIFFUSIVE FLUX

In porous medium, geometry imposes constraints:

∂C ∂C
JD = − τ DO n = −D*n
∂x ∂x

τ = tortuosity factor
D* = effective diffusion coefficient

Factor n must be included since diffusion is only in pores


TORTUOSITY

Solute must travel a tortuous path, winding through


pores and around solid grains
2
⎛L ⎞
Common empirical expression: τ = ⎜⎜ ⎟⎟
⎝ Le ⎠
L = straight-line distance
Le = actual (effective) path

τ ≈ 0.7 for sand


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

C
B

C
B
A A

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 diffusion—i.e., that flux is
proportional to concentration gradient:

∂C
JM = −DM n
∂x
Dispersion coefficient, DM = αL u

αL = longitudinal dispersivity (units of length)


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
Source: U.S. Geological Survey, Cape Cod Toxic
Accessed May 14, 2004.
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):

J =JA +JD +JM


∂C ∂C
J = nuC − D * n − DM n
∂x ∂x
∂C
J = nuC − D H
∂x

DH = D* + DM = τ DO + αL u
= hydrodynamic dispersion
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

Change in
contaminant Flux in less Sources and
mass with flux out of sinks due to
time REV reactions

∂C T (1)
= −∇•J ± S/S
∂t
∂C T ∂J
= − ± S/S (2)
∂t ∂x
TRANSPORT EQUATION
CT = total mass (dissolved mass plus mass adsorbed to
solid) per unit volume
= ρb CS + n CW = ρb CS + n C (3)
Note: W subscript dropped for convenience and for
Consistency with conventional notation

Substitute Equation 3 into Equation 2:


∂ (ρbCS ) ∂ (nC) ∂ ⎛ ∂C ⎞ (4)
+ =− ⎜ nuC − DHn ⎟ ± S/S
∂t ∂t ∂x ⎝ ∂x ⎠
↑ no solid phase in flux term
TRANSPORT EQUATION
CS = Kd C by definition of Kd

Assume spatially uniform n, ρb, Kd, u, and DH and no S/S

∂C ∂C ∂ C 2
(ρbK d + n) = −nu + nDH 2 (5)
∂t ∂x ∂x
∂C u ∂C DH ∂ C
2
=− + (6)
∂t ρ
⎛ b dK + n ρ
⎞ ∂x ⎛ b d K + n ⎞ ∂x 2
⎜ ⎟ ⎜ ⎟
⎝ n ⎠ ⎝ n ⎠
TRANSPORT EQUATION
“Retardation factor”, Rd
ρbK d + n ρbK d (7)
= 1+ = Rd
n n
Substituting Equation 7 into Equation 6:

∂C u ∂ C DH ∂ C 2
(8)
=− +
∂t R d ∂x R d ∂x 2
Effect of adsorption to solids is an apparent slowing of transport
of dissolved contaminants
Both u and DH 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
- x

x-a x+a

[
[
Relative Concentration C/C0 1.0

0.8

0.6

0.4

0.2

0.0

t1 t2 t0

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 C0 .
0

Adapted from: Fetter, C. W. Contaminant Hydrogeology.


New York: Macmillan Publishing Company, 1992.
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:
Co ⎛ R d x − ut ⎞
C(x, t ) = erfc⎜ ⎟
2 ⎜ 4R D t ⎟
⎝ d H ⎠

Where Co = C(x=0, t) = constant concentration at


source location x = 0
Solution is a front moving with velocity u/Rd
1.0
0.9
0.84
0.8

Relative Concentration C/C0


0.7
0.6
0.50
0.4
0.3

Mean
0.2
0.16
0.1
0.0 x

+s s

x = ut/Rd

The profile of a diffusing front as predicted by the complementary error function.

Adapted from Fetter, C. W. Contaminant Hydrogeology.


New York: Macmillan Publishing Company, 1992.
Moving front of contaminant from constant source

10

9 C0 = 10
u=1
8 DH = 0.1
Rd = 1
Concentration, C(x,t)

7
t=1 t=3 t=5
6 ut = 1 ut = 3 ut = 5
5

0
0 1 2 3 4 5 6 7 8 9
Distance, x
Moving front of contaminant from constant source
Effect of dispersion coefficient
Effect of Rd on moving front of contaminant
Effect of retardation

10

9 C0 = 10
t=3 t=3 u=1
8 ut = 3 ut = 3 DH = 0.1
Rd = 2 Rd = 1
Concentration, C(x,t)

0
0 1 2 3 4 5 6 7 8 9
Distance, x
1-D SOLUTIONS

Transport of a Conservative Substance from Pulse and Continuous Sources

Dimensions Pulse Input of Mass M .


Continuous Input of Mass Per .
Continuous Input of Mass Per
Unit Time M Starting at Time t = 0 Unit Time M in Steady State

.
[ [ ( (
.
2
1-D C= M exp - (x-vt) C = M erfc
x-vt
C= M ( for x > 0 (
. 1/2 1/2
2np t D x 4Dxt 2nv 2 Dx t nv
M, M are instantaneous
or continuous plane
sources x=0 v x=0 v x=0 v
M
M to ∞
L2
t=0 t = t1
.
M
M 2 Mass Front at Mass
L T
input here time t input here

Adapted from: Hemond, H. F. and E. J. Fechner-Levy. Chemical Fate and Transport in the Environment.
2nd ed. San Diego: Academic Press, 2000.
2-D SOLUTIONS

Transport of a Conservative Substance from Pulse and Continuous Sources

Dimensions Pulse Input of Mass M . Input of Mass Per


Continuous . of Mass Per
Continuous Input
Unit Time M Starting at Time t = 0 Unit Time M in Steady State

. 2-D
M, M are instantaneous
or continuous line
C= M exp
4np t Dx Dy [
(x-vt)2 y2
+
4Dx t 4Dy t [ C= M
.
4np 1/2 (vr)1/2 Dy [ [ ( (
exp (x-r)v erfc r-vt
2D x 2 Dx t
C=
1/2
2np (vr)
.
M
1/2
Dy [ [
exp (x-r)v
2D x

sources

M [[
M
L t=0
y
t =
v
t1
y
v
Plume at time t
y
v

.
[ [
M x x to ∞
M x
L-T

Adapted from: Hemond, H. F. and E. J. Fechner-Levy. Chemical Fate and Transport in the Environment.
2nd ed. San Diego: Academic Press, 2000.
3-D SOLUTIONS
Transport of a Conservative Substance from Pulse and Continuous Sources

Dimensions Pulse Input of Mass M . Input of Mass Per


Continuous . of Mass Per
Continuous Input
Unit Time M Starting at Time t = 0 Unit Time M in Steady State

. 3-D
M, M are instantaneous
C=
8np 3/2 3/2
t
M
Dx Dy D z
C=
.
M
8np r DyD z [ [ ( (
exp (x-r)v erfc r-vt
2D x 2 Dx t
C= M
.
4np r DyD z [ [
exp (x-r)v
2D x

[ [
or continuous point (x-vt)2 y2 z2
sources exp - + +
4Dx t 4Dy t 4Dz t
M [[
M
L
v z y z y v
. v
[ [
M z y
M
T
x
to ∞
t=0 t = t1 Plume at time t

Adapted from: Hemond, H. F. and E. J. Fechner-Levy. Chemical Fate and Transport in the Environment.
2nd ed. San Diego: Academic Press, 2000.