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- MT: Diffusion With a Homogeneous Chemical Reaction
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Assumptions

1. Equivalent porous medium (epm)

(i.e., a medium with connected pore space

or a densely fractured medium with a single

network of connected fractures)

2. Miscible flow

(i.e., solutes dissolve in water; DNAPLs and

LNAPLs require a different governing equation.

See p. 472, note 15.5, in Zheng and Bennett.)

3. No density effects

Density-dependent flow requires

a different governing equation. See

Zheng and Bennett, Chapter 15.

Figures from Freeze & Cherry (1979)

Derivation of the

Advection-Dispersion Equation (ADE)

s

h h

KA Q

=

1 2

Darcys law:

h

1

h

2

q =Q/A

advective flux

f

A

= q c

h

1

h

2

f =F/A

h

1

h

2

f

A

= advective flux = qc

f = f

A

+ f

D

How do we quantify the

dispersive flux?

s

c c

A D F d Diff

=

1 2

How about

Ficks law of diffusion?

where D

d

is the effective

diffusion coefficient.

Ficks law describes diffusion of ions on a

molecular scale as ions diffuse from areas of

higher to lower concentrations.

Dual Porosity

Domain

Figure from Freeze & Cherry (1979)

We need to introduce a law to describe

dispersion, to account for the deviation of

velocities from the average linear velocity

calculated by Darcys law.

Average linear velocity

True velocities

We will assume that dispersion follows

Ficks law, or in other words, that dispersion

is Fickian. This is an important assumption;

it turns out that the Fickian assumption is not

strictly valid near the source of the contaminant.

s

c c

D fD

=

1 2

porosity

Mathematically, porosity functions as a kind of

units conversion factor.

Porosity ()

for example:

q c = v c

Later we will define the dispersion coefficient

in terms of v and therefore we insert now:

s

c c

D fD

=

1 2

Assume 1D flow

and a line source

Case 1

c v c

x

h h

K c q f x x A =

= = ] [

1 2

Advective flux

x

c c

D f x D

=

1 2

Dispersive flux

Assume 1D flow

D is the dispersion coefficient. It includes

the effects of dispersion and diffusion. D

x

is sometimes

written D

L

and called the longitudinal dispersion coefficient.

porosity

Case 1

Assume 1D flow

and a point source

Case 2

f

A

= q

x

c

Advective flux

D

x

represents longitudinal dispersion (& diffusion);

D

y

represents horizontal transverse dispersion (& diffusion);

D

z

represents vertical transverse dispersion (& diffusion).

) (

1 2

x

c c

D f x Dx

=

) (

1 2

z

c c

D f z Dz

=

Dispersive fluxes

) (

1 2

y

c c

D f y Dy

=

Figure from Freeze & Cherry (1979)

Continuous point source

Instantaneous point source

Average

linear

velocity

center of mass

Figure from Wang and Anderson (1982)

Instantaneous

Point Source

transverse

dispersion

longitudinal dispersion

Gaussian

Derivation of the ADE for

1D uniform flow and 3D dispersion

(e.g., a point source in a uniform flow field)

f = f

A

+ f

D

Mass Balance:

Flux out Flux in = change in mass

v

x

= a constant

v

y

= v

z

= 0

Porosity ()

There are two types of porosity in transport problems:

total porosity and effective porosity.

Total porosity includes immobile pore water, which contains

solute and therefore it should be accounted for when

determining the total mass in the system.

Effective porosity accounts for water in interconnected pore

space, which is flowing/mobile.

In practice, we assume that total porosity equals effective

porosity for purposes of deriving the advection-dispersion eqn.

See Zheng and Bennett, pp. 56-57.

Definition of the Dispersion Coefficient

in a 1D uniform flow field

v

x

= a constant

v

y

= v

z

= 0

D

x

=

x

v

x

+ D

d

D

y

=

y

v

x

+ D

d

D

z

=

z

v

x

+ D

d

where

x

z

are known as dispersivities. Dispersivity is

essentially a fudge factor to account for the deviations of

the true velocities from the average linear velocities

calculated from Darcys law.

Rule of thumb:

y

= 0.1

x

;

z

= 0.1

y

t

c

x

c

v

z

c

D

y

c

D

x

c

D z y x

2

2

2

2

2

2

ADE for 1D uniform flow

and 3D dispersion

No sink/source term; no chemical reactions

Question: If there is no source term, how does

the contaminant enter the system?

t

c

x

c

v

x

c

D

2

2

Simpler form of the ADE

Uniform 1D flow; longitudinal dispersion;

No sink/source term; no chemical reactions

There is a famous analytical solution to this form of the

ADE with a continuous line source boundary condition.

The solution is called the Ogata & Banks solution.

Question: Is this equation valid for both point

and line source boundaries?

Effects of dispersion on the concentration profile

(Zheng & Bennett, Fig. 3.11)

no dispersion

dispersion

(Freeze & Cherry, 1979, Fig. 9.1)

t1 t2 t3

t4

Effects of dispersion on the

breakthrough curve

Figure from Wang and Anderson (1982)

Instantaneous

Point Source

Gaussian

Breakthrough

curve

Concentration

profile

long tail

Figure from Freeze & Cherry (1979)

Microscopic or local scale dispersion

Macroscopic Dispersion

(caused by the presence of heterogeneities)

Homogeneous aquifer

Heterogeneous

aquifers

Figure from Freeze & Cherry (1979)

Dispersivity () is a measure of the

heterogeneity present in the aquifer.

A very heterogeneous porous medium

has a higher dispersivity than a slightly

heterogeneous porous medium.

Dispersion in a 3D flow field

x

z

x

z

global local

K

xx

K

xy

K

xz

K

yx

K

yy

K

yz

K

zx

K

zy

K

zz

K

x

0 0

0 K

y

0

0 0 K

z

[K] = [R]

-1

[K] [R]

K =

z

h

K

y

h

K

x

h

K q

z

h

K

y

h

K

x

h

K q

z

h

K

y

h

K

x

h

K q

zz zy zx z

yz yy yx y

xz xy xx x

=

Dispersion Coefficient (D)

D = D + D

d

D

xx

D

xy

D

xz

D

yx

D

yy

D

yz

D

zx

D

zy

D

zz

D =

In general: D >> D

d

D represents dispersion

D

d

represents molecular diffusion

z

c

D

y

c

D

x

c

D f

z

c

D

y

c

D

x

c

D f

z

c

D

y

c

D

x

c

D f

zz zy zx Dz

yz yy yx Dy

xz xy xx Dx

=

In a 3D flow field it is not possible to simplify the dispersion

tensor to three principal components. In a 3D flow field,

we must consider all 9 components of the dispersion tensor.

The definition of the dispersion coefficient is more

complicated for 2D or 3D flow. See Zheng and Bennett,

eqns. 3.37-3.42.

D

x

=

x

v

x

+ D

d

D

y

=

y

v

x

+ D

d

D

z

=

z

v

x

+ D

d

Recall, that for

1D uniform flow:

General form of the ADE:

Expands to 9 terms

Expands to 3 terms

(See eqn. 3.48 in Z&B)

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