4.

Course Number: CE 394K

Course Title: Groundwater Pollution and Transport
Course Instructor: R.J. Charbeneau

Subject: Mass Transport Processes

Topics Covered:
1. General mass transport equation
2. Advection and diffusion transport
3. Advection-dispersion transport
4. Characterization of aquifer dispersion
Reading: Chapter 7, Chapter 8

4.2

Mass Transport Processes

1. Advection
2. Diffusion
3. Mechanical Dispersion

Mass Flux (Vector)

J
mass/area/time

Mass
Flux
~
J=

= Advection + Diffusion + Dispersion

~
qc

n D s c

~
~
n Dmd c

4.3

Mass Transport
^
n
J
dA
~
& = Jn dA
Mass Transport: m
(mass per time crossing the surface)

4.4

Bulk (Total) Concentration

Water

NAPL

Air

m or CT

m = w C w + a C a + o C o + b C s

4.5

Continuity Equation (CV)

out

in

The net rate of mass

increase is equal to
the net mass flux
into the region plus
the increase in mass
within the region due
to biotic and abiotic
processes

d m dV = J~n dA+ S + dV

dt CV
CS
CV

4.6

Continuity Equation (PDE)

Control Volume

Point

m + J~ = S +
t
This is the starting point!!

4.7

Advection-Dispersion Equation
~
m
~
2
~

+ (q wC w ) DsT m nDmd C w + m = 0

t
Mass partitioning from all phases
Aqueous advection transport dominates other advection

components

Multiphase diffusion (primarily air-phase volatilization and

water-phase transport through geo-liners and sorption sites

during mass-transfer kinetics)

Mechanical dispersion in aqueous phase

Degradation (first-order) based on total concentration

4.8

Advection Transport
Mass carried forward with the groundwater flow
Mass transport rate depends on the local
concentration and the specific discharge (volume
flux; Darcy velocity): Jadv = qw Cw
Significant interest is generally placed on
distribution of subsurface flow paths and travel
times along these paths (see textbook for
analytical treatment of flow paths streamlines
and travel times)

4.9

Advection Transport Travel

Time (Vs = seepage velocity)
streamline
vs

Water Travel Time:

s

dt = ds/vs

Contaminant Travel Time:

dtc = R ds/vs

4.10

Method of Characteristics
Advection Transport:

C
C
R
+ vs
= R C
t
s

Characteristic Equations
vc

vs

dt ds
dc
=
=
R v s Rc

streamline

ds v s
=
dt R
tc = R ds vs

&

all streamlines,
all solute particles

Lagrangian (a solute

particle along a single

streamline)

dc Rc
=
ds
vs

C (s ) = C (0 ) exp R ds vs

4.11

MODPATH
Model for calculating pathlines and travel
times from MODFLOW output files
Need to first run MODFLOW with cell-by-cell
water budget and head output
(e.g.,CLASS.BUD and CLASS.HED)

4.12

Calculation of Flow Field

i,j,k-1/2

Cell i, j, k

Cell-by-Cell budget file saves

face discharge for each cell:
Qi,j-1/2,k , Qi,j+1/2,k , etc.

i,j+1/2,k

i+1/2,j,k

v x1 =

i,j,k+1/2

Qi , j 1/ 2,k
n y i zk

Face seepage velocity and cell interior

velocity gradients are then determined:
; v x2 =

Qi , j +1/ 2,k
n y i zk

Within the cell, vx depends only on x:

vx(x) = vx1 + Ax (x x1)

Linear Interpolation

v x 2 v x1
Ax =
x j

Etc. for
y and z.

4.13

Streamline Characteristic Equation

From Fluid Mechanics,
streamlines are lines
parallel with the velocity
vector.

dx dy dz
=
=
= dt
vx vy vz

X-Component: integrate from initial point xp where vx = vx(xp)

dx
= dt
v x1 + Ax (x x1 )

1 v x1 + Ax (x x1 )
ln
= t

Ax
v xp (x p )

This gives

1
[
x = x1 +
v xp (x p ) exp(Ax t ) v x1]
Ax
Similar results are found for Y- and Z-components.

4.14

Approach
xj

With inflow location (xp,yp,zp), find

minimum travel time to outflow face from

1 v x 2
= t
ln

Ax v xp

yi

1 v y 2
ln
= t

Ay v yp

(xp,yp)
Using the smallest t, find the outflow location from

1
[
x = x1 +
v xp (x p ) exp(Ax t ) v x1]
Ax

Etc.

This becomes the starting point for the next cell.

4.15

ModPath Interactive Input

When you run MODPATH, input is provided both through MFI and
interactively.

4.16

ModView
MODVIEW (Model Viewer) provides graphical output

4.17

ModView
With MODVIEW you can control what features
are shown, and how they are shown.

4.18

Diffusion Transport
Diffusion Transport with Decay
c
R
= D s 2 (c ) R c
t
Effective soil diffusion coefficient
Issues:
1.

Magnitude of molecular diffusion coefficient, Dm

2.

How does Dm relate to Ds (Effective soil diffusion

coefficient)

3.

Significant (and useful) solutions to the diffusion

transport equation

4.19

Magnitude of Diffusion Coefficients

Gases
2
Dm (G ) =
3 p d2

( T )3
3 m

10 1 cm 2 s

Liquids
Dm (L ) =

T
10 5 cm 2 s
3d

Comparison:

Dm (G )
10 4
Dm (L )

4.20

Molecular Diffusion in Soil

Le

Tortuosity:

L
=
Le

ave

Effective Soil Diffusion Coefficient (Take One):

D s = Dm
Millington and Quirk (1961):

n D s = n4 3 Dm

4.21

Diffusion in Multiphase Systems

Definition of Total
Diffusion Flux:
~
JT = DsT m
1

D sT

n D sw n D sa n D so
=
+
+
Bw
Ba
Bo
~0

Benzene in Soil
0.1

DsT/Dm (g)

Mass Transport through all

phases:

0.01
0.001

a2 Dma
n Ba
10 3

D sT

0.0001
0.00001
0

0.2

0.4

0.6

Air Saturation

0.8

4.22

Point Release of Mass

C

to

= D s 2 (c )
t

t1
t2
r

Ds = Ds/R

M (n R )
r 2

c (r , t ) =
exp
32

4 D t
4
D
s t

1D Solution
2

M (n R )
x

c (x , t ) =

exp
12

4 D t
D
4
s t

3D Solution

Comparison?

4.23

Mass Flux from a Surface

2c
c
R = Ds 2
t
z

Co
Co

t1
t2

C(z,t)

M(t)/A

Solution

z
c( z , t ) = co erfc
4D t
s

c(z = 0, t )
M (t )

= n R c( z , t ) dz = J ( z = 0, t ) dt = n Ds
dt
z
A

0
0
0

Cumulative Influx:

M (t )
= n R co
A

4 Ds t

4.24

Special Functions
Error Function
X

2
2
erf (X ) =
e d
0

Complimentary Error Function

X

2
2
2
2
erfc (X ) = 1
e
d =
e
d
0
X
erf(X) + erfc(X) = 1
erfc(-X) = 1 + erf(X) = 2 erfc(X)

Note: Excels
erf( ) and erfc( )
functions do not
work for
negative
arguments

4.25

Error Function (and Complementary)

2
erfc(x)

erfc(x) and erf(x)

1.5

erf(x)

0.5

0
-3

-2

-1

-0.5

-1
Argument x

4.26

Using Error Functions with Excel

Under Tools/Add-Ins
select the Analysis
TookPak. This will allow
you to use Erf() and
Erfc(), but they work
only for positive
arguments.

4.27

Visual Basic Module for Excel

Function erfc(x)
tmp = Abs(x)
Pi = 3.141592654
If tmp > 3 Then
f1 = (1 - 1 / (2 * tmp ^ 2) + 3 / (4 * tmp ^ 4) - 5 / (6 * tmp ^ 6))
fun = f1 * Exp(-tmp * tmp) / (tmp * Sqr(Pi))
If tmp = x Then
erfc = fun
Else
erfc = 2 - fun
End If
Else
tmp2 = 1 / (1 + 0.3275911 * tmp)
tmp3 = 0.254829592 * tmp2 - 0.284496736 * tmp2 ^ 2 + 1.421413741 * tmp2 ^ 3
tmp4 = -1.453152027 * tmp2 ^ 4 + 1.061405429 * tmp2 ^ 5
fun = (tmp3 + tmp4) * Exp(-tmp * tmp)
If tmp = x Then
erfc = fun
Else
erfc = 2 - fun
End If
End If
End Function

4.28

Diffusion-based Volatilization Model

M(t)/A
t1

t0

t2

mo
z

m
2m
= D sT 2
t
z
Bulk Concentration:

z
m(z, t ) = mo erf
4D
sT

Cumulative Volatilization

M(t )
= mo
A

4 D sT t

Notation Note:

D sT

n D sa n K H D sa
n K H D sa
=
=
w + a K H + o K o + b K d
Ba
Bw

Compare
with Ds

4.29

Volatilization Moving
Boundary Model
J vol

mo

D sT mo
=
y

Soil
Surface
Pollutant
Depth

Continuity:
mo
dy
mo
= J vol = D sT
dt
y

Solution (with y(0) = 0)

y (t ) = 2 D sT t

Cumulative Volatilization
M(t )
= mo y (t ) = mo 2 D sT t
A
Compare Solutions

4.30

Advection-Dispersion Transport:
Laboratory Column Studies
Cout(t)
L

Mathematical Model
Conservative Tracer
C
C
2C
+v
D 2 = 0
t
x
x

C(x,t)

Initial Conditions: C(x,0) = 0

Boundary Condition (Inlet): ??
Boundary Condition (Outlet): ??

Cin(t)

C(L, t ) = ? ;

C
(L, t ) = ?
x

4.31

Type-One BC Dirichlet
C
2C
C
+v
D 2 = 0
t
x
x
C(0, t ) = Co

C(x , t ) = 0

Inlet (x = 0)

Concentration
Fixed

x + v t
x vt
C(x, t ) 1
xv

= erfc
+ exp erfc

Co
2
D
4D t
4D t

4.32

Type-Three BC - Cauchy
C
2C
C
+v
D 2 = 0
t
x
x

Mixing Reservoir, C = Co

q Co = q C n D
x x =0

Advection +
Dispersion
x

(x vt )2 vx v 2 t
x vt
x + v t
C(x, t ) 1
4v 2 t
xv

exp
exp
= erfc
+
1 +
+
erfc

Co
2
4Dt
D
D
D
D
4D t
4 D t

4.33

Type-Two BC
C
C
2C
D 2 = 0
+v
t
x
x

n C(x, t ) dx = q Co t

xvt
x + v t
C(x, t ) 1
xv

exp

= erfc
erfc
Co
2
D
4 D t
4D t

4.34

Simple BC (see textbook for

discussion of other solutions)
C
C
2C
D 2 = 0
+v
t
x
x
C(x<0,t=0) = Co
C(x>0,t=0) = 0
xvt
C(x, t ) 1

= erfc
Co
2
4D t

t=0
Co

C(x,t)
t = 0+

t = t1
x=0

4.35

How do you choose a model?

Inlet Concentration (v = 0.5 m/d, D = 0.05 m2/d)
1
0.9
Concentration C/Co

0.8
0.7
0.6
0.5

Simple

0.4

First-Type

0.3

Second-Type

0.2

Third-Type

0.1
0
0

0.5

1.5
Time (Days)

2.5

4.36

Model Comparison
Effluent Concentration (L = 0.5 m)
1
0.9
Concentration C/Co

0.8
0.7
0.6
0.5

Simple

0.4

First-Type

0.3

Second-Type

0.2

Third-Type

0.1
0
0

0.5

1.5
Time (Days)

2.5

4.37

Non-dimensional Transport Equation

C
C
2C
D 2 = 0
+v
t
x
x

X = x/L

T = t v/L

Peclet Number PL = L v/D

C C 1 2C
+

=0
2
T X PL X

Model Effluent (X = 1) Equation:

P (1 T )
C(T ) 1

= erfc L
Co
2
T
4

4.38

Scaled-time Parameter
Scaled Time

T 1
=
2T

T=0

T=

C( ) 1
P
= erfc L = N( PL )
Co
2
2

Cumulative Normal
Distribution Function

Conclusion: Breakthrough [C(t) at x = L] depends only

on time and the (column) Peclet number, and the curve

will be a symmetric function of scaled time

4.39

Experimental Results: Conclusions?

1
C(t)/Co

Same soil,
same column,
different flow
rates

v2 < v 1

v1

t
1
C()/Co

Theoretical
Curve

Same soil,
same column,
different flow
rates

4.40

Same Peclet Number?

C( ) 1
P
= erfc L = N( PL )
Co
2
2

D L
=
aL
v PL

Same curve with

different velocities
parameter PL must be
the same for both
experiments!!

Soil Characteristic, Longitudinal

Dispersivity (L)

Mechanical Dispersion:
D = aL v

4.41

Hydrodynamic Dispersion
Dispersion + Diffusion
D = Dm + aL v

How Large is the Longitudinal Dispersivity?

Grain-size Peclet Number: Pd = v d/Dm
mean grain size

Laboratory Experiments (200 < Pd < 20,000)

aL = (1.8 +/- 0.4) d

4.42

Characterization: Diffusion vs.

Mechanical Dispersion
Point Release: Molecular Diffusion
C(x,t)

C
2C
= Ds 2
t
x

t=0

C(x,0 ) =

M
( x x o )
n

See Example 7.5.1

t1
C(x, t ) =

t2
xo

2 = 2 Ds t
Einstein, 1905

(x x o )2
Mn

exp

4Ds t
4Ds t

Compare with Normal Density Function

(x; , ) =

(x )2

exp
2

2
2
2

4.43

Characterization: Mechanical
Dispersion
C
C
2C
D 2 = 0
+v
t
x
x
t1

D = aL v

Stationary

t2

Moving
coordinate
system:
v

C
2C
=D 2
t
x

( x ' )2
Mn

exp
C(x, t ) =

4Dt
4
Dt

x = x v t
t = t
C(x,0 ) =

M
( x )
n

2 = 2 aLv t = 2 aLXm

4.44

Spread of a Concentration Front

Xm
x=vt

4
Diffusion:
Dispersion:

= 2 Ds t

= 2 aL Xm

4.45

Mechanical Dispersion
Field Experience
Types of Field Tracer Tests

Natural Gradient Tracer Tests

Single-well Injection Tests
Single-well Injection-production Tests
Multiple Well Tests

4.46

Radial Flow from a Well

C/Co
1
0.5

Monitoring
Well
Model:
r R
C(r, t ) 1

= erfc
2 2
Co
2

R
R=

Qt
nb

4.47

Tracer-Front Dispersion
1. Longitudinal Dispersion
2. Divergence of Flow Lines
2 =

r R
C(r, t ) 1

= erfc
2 2
Co
2

2
aL R
3

r Qt
C(r, t ) 1
nb
= erfc
4
Co
2
Qt
aL

nb
3

4.48

Pickens and Grisak (1981)

4.49

Site Layout
Multilevel Sampling

4.50

Laboratory Tests
P (1 T )
C(T ) 1

= erfc L
Co
2
T
4

4.51

Cross-Sections for Single Well

Tests SW1 and SW2

4.52

Single-Well
Breakthrough
Tests
Test SW1:
distances
1 m, 2 m,
3 m, 4 m
Test SW2:
distances
0.36 m,
0.66 m,
2.06 m

4.53

Injection-Withdrawal Tests

Vp

Vi
C 1
= erfc

12
Co 2

16 aL
Vp Vp
1

2 1

Vi
Vi
3 Rm

4.54

Summary Results

4.55

Hydraulic Conductivity
Distribution

4.56

Scale-Dependent Dispersivity

4.57

Transverse Dispersion
M

2C
C
D 2 = 0 ; C(0, y ) = M (y )
v
x
y

C(x, y )
M
y

=
exp
D
Co
D
4 x
4 x

v
v

Laboratory: Pd > 100

C(x,y) independent of v
Transverse
Dispersivity:

D/v = aT

aT = 0.04 d
Laboratory

4.58

Mechanical Dispersion Tensor

DL = aL v

Uniform
Flow

DT = aT v

Dij = a T v ij + (aL a T )

vi v j
v

Non-uniform Flow Field

4.59

Components
2

2
2
vy
vx
vz
+ aT
+ aT
Dxx = aL
v
v
v
2

2
2
vy
vx
vz
+ aL
+ aT
D yy = aT
v
v
v

Dxy = D yx = (a L aT )

vx v y
v

etc.

~

C
C

C
~

+ L + Dzz
D C = Dxx

+ Dxy
x

z
z
y
x x

Nine Separate Terms!!

4.60

Scale Effects
Longitudinal Dispersivity (m)

1000

100

10

High
Intermediate

0.1

Low
0.01
1

10

100

1000

10000

100000

Scale of Test (m)

Field Data (Gelhar et al., 1992)

4.61

Models for Scale Effects

EPA (1986):
aL = 0.1 Xr

aT = 1/3 aL

av = 1/80 1/10 aL

EPACML: (for receptor at Xr = 500 ft)

Class
1
aL (m)
0.1-1
Probability 0.1

aL (Xr ) = aL (500 ft )

Xr
500

2
1-10
0.6

; aT =

1
aL
8

3
10-100
0.3

; av =

1
aL
160

4.62

Natural Gradient Tracer Test

Borden Landfill Site EPA, Stanford, Waterloo

4.63

Site Location

4.64

Site Layout

4.65

K-Distribution

- ln(K) ; K in cm/s

4.66

K-Distribution

4.67

Field Description
Geostatistics
Second-order Model:
Mean
Variance
Spatial-correlation

4.68

Basic Statistics of the Field

K-distribution, mean,
variance and spatial
correlation:

4.69

Experiment
Tracers
Chloride ion (892 mg/L; 10,700 g)
Bromide ion (324 mg/L; 3,870 g)

Organic Solutes
Bromoform (0.032 mg/L; 0.38 g)
Carbon tetrachloride (0.031 mg/L; 0.37 g)
Tetrachloroethylene (0.030 mg/L; 0.36 g)
1,2-Dichlorobenzene (0.332 mg/L; 4.0 g)
Hexachloroethane (0.020 mg/L; 0.23 g)

4.70

Tracer Experiments

4.71

Vertical Dispersion

Chloride Distribution

4.72

Vertical Averaging
Choride
Time = 462 d

4.73

Spatial Distribution
Bromide:
1038 days

4.74

Retardation

4.75

Estimation from Spatial Moments

2

= 2D t
1 d 2
D=
2 dt

Xc

D
ai =
vm
vm

dX c
=
dt

4.76

Spatial Moments
Bromide - xx

80

Bromide - yy

Spatial Variance, (m )

90

70

Chloride - xx

60

Chloride - yy

50
40
30
20
10
0
0

200

400

600

800

Elapsed Time (d)

1000

1200

4.77

Moment Analysis
Variance increase gives aL = 0.36 m
and aT = 0.091 m, based on an average
velocity of v = 0.091 m/d
Theory: Far-field dispersivity
aL = 2 ln(K ) ln(K )
Data gives far-field
value aL = 0.59 m