Section #2

Filtration Theory

Part #2
Scale Up
Transport Basics
Physical processes that control the transport of solutes dissolved in
groundwater can be divided into three (somewhat related) mechanisms:
Advection
Bulk displacement of solute (tracer) due to flowing groundwater
Driving force is the hydraulic gradient
Molecular Diffusion
Transport to intrinsic thermal energy of solutes and the
accompanying Brownian motion
Transport along concentration gradient
Mechanical Dispersion
Mixing process due to small-scale variations in velocity field that are
not described by advection
Position of the Advective (plug-flow) front
The average position of tracer molecule released at a point X=Xo at time t=0 can be
computed as follows:
X t
dx
dt
= v or dx = vdt or dx = vdt
Xo 0

If flow is steady and uniform (i.e. v is constant) then

X (t ) = X o + vt
Given the above, let us now consider a 1-D column of porous medium into which we
continuously inject a tracer.

Inject at Co continuously
X=0 X=L
 After some time, t, the concentration profile in the column might be as shown below:
Position of advective (plug-flow) front
Co

Co/2

Actual observed curve

The advective front is a sharp front; however, the actual concentration profile is
not sharp in that the concentration gradually declines from C=Co to C=0 over
some distance.
The lack of a sharp front is due to hydrodynamic dispersion that is discussed
below.
In short, the above curve suggests that some tracer molecules are traveling faster
than while some are traveling slower than.
Mechanical Dispersion
When variations exist in the velocity field, individual tracer molecules will move
different distances in a given time and this tends to create a diffuse front rather
than a sharp front.
In a porous medium there are many opportunities for the velocity to vary from one
point to the next.
For example, across a pore throat, viscous flow theory suggests that the
velocity should be a maximum in the center of the pore and should approach
zero at the grain boundary as illustrated below on the left.

Another source of variations might be due to spatial variations in pore size as

shown on the right.
 We could get an idea of the relative concentration distribution by counting the
number of particles within each of the panels (of width DX) after time t and
dividing by the total number released as illustrated below.

Relative 0.3
frequency
of particles

0.1
X
vt

As we get further and further removed from one expects to find

fewer and fewer particles since the probability that the local
velocity will be small
Molecular Diffusion
The net movement of solutes due to Brownian motion (resulting from thermal energy) is
called molecular diffusion. The mass flux due to diffusion is given by Ficks 1st law as:

C
Jd = De
X
= volumetric water content (porosity if saturated)
De = effective diffusion coefficient [L2 /T]

Ficks 2nd law of diffusion for a porous media is:

C 2C
= De
t X 2

(time rate of change of concentration) (curvature of concentration)

 Consider a diffusing solute in a column of infinite length with the left end
maintained at C=1

The diffusion equation can also be solved for a column of finite length where the ends
of the column are maintained at constant concentrations
At steady state, i.e. when:

then the curvature of the concentration distribution equals 0:

Thus, the steady state concentration distribution must be linear.

For a column with constant concentrations at each end, the concentration must
change linearly with distance between the two ends (at steady state).
Advection dispersion equation
Derivation of the advection-dispersion equation is performed below for a
one-dimensional system (e.g. column experiment), via mass balance on a
representative elementary volume (R.E.V.) of aquifer material:

dispersion in dispersion out

C C
D D C + dX
X X X
dz

advection in advection out

C
V (C ) dy V C + dX
dx
X

where is the volumetric water content (L3water/L3R.E.V.), which is equal to the

porosity under saturated conditions. V is the velocity of groundwater.
Advection dispersion equation - more
Recall:

accumulation = input - output

C C
dx dy dz = + vCdy dz + D dy dz
t x
C C
v C + dx dy dz D C + dx dy dz
x x x

C C C
dx dy dz = v dx dy dz + D dx dy dz
t x x x

C C 2C
dx dy dz = v dx dy dz + D 2 dx dy dz
t x x

M chem L3water LR .E .V . M chem L3water L2R .E .V . M chem L3water

L3
R . E .V . = L3
R . E .V . + L3
R . E .V .
L3water T L3R .E .V . T L3water LR .E .V . L3R .E .V . T L3water L2R .E .V . L3R .E .V .
Advection dispersion equation breakthrough curves
C C 2C
= v + D 2
t x x
advection dispersion

Which is the advection dispersion equation in one dimension. And it

describes the change in the concentration w.r.t time of a given chemical in
an element of aquifer due to advection and dispersion of the chemical in
groundwater.

If one considers a 1-dimensional system such as the columns shown

below, the equation above can describe the change in concentration over
time at a given point in the column.

soln water

soln water
Initial and Boundary Conditions
In order to solve the advection dispersion equation we must have
initial and boundary conditions. For the initial condition we simply
must specify the concentration at all points in space at time equal to
zero:
C(x,y,z,t) = f(x,y,z)
For boundary conditions we have 3 choices:
1. Specify C on boundary; this is also known as 1st type or Dirichlet
boundary conditions
2. Specify value of the derivative of C normal to the boundary; this
is also known as 2nd type or Neuman boundary condition
3. Specify both the value of C and its derivative on the boundary;
this is known as 3rd type, mixed, or Cauchy boundary condition
The conditions specified on the boundary can in general be a
function time.
Consider the following examples of how these various boundary conditions get applied.

1.Semi-infinite column

1. Sandbox in 2D with internal source (Co)

2nd type on left, top, and bottom, 1st type on right as X approaches infinity
3. Semi-infinite column with a well mixed reservoir at the inlet (left) boundary
Ogata Banks Spreadsheet
 Inserting reactions into advection dispersion equation
How does one account for reactive transport? Examining the advection
dispersion equation:

Cwater
cont
Cwater
cont
2 Cwater
cont
= v +D
t x x 2

One can recognize that reactions that remove the compound from the
aqueous phase will decrease the aqueous phase concentration:

Cwater
cont
Cwater
cont
2Cwater
cont
= v +D G
t x x 2

where G is a sink term representing any of the reactions listed previously.

Production of a compound is also possible (e.g. by-product of degradation

of another compound), in which case the term (source term) that describes
that particular process would be preceded by a positive sign.
Irreversible and reversible reactions
The form of the source or sink term depends on the particular reaction
process, which can be grouped into two main categories:
1) Irreversible
a. Radioactive decay
b. Biodegradation
c. Filtration (generalized as irreversible)
d. Volatilization (usually, since compounds disperse once in
vadose zone)
2) Reversible
a. Precipitation (via dissolution)
b. Partitioning
c. Adsorption

The above groupings are representative only, since all processes except
radioactive decay and biodegradation may be reversible or irreversible
depending on context.
Reversible (equilibrium) and Linear Reactions
Derivation of R
Reversible processes involve two-directional exchange of the compound
between the aqueous phase and the other phase of interest. For sorption,
the compound is exchanged between water and sediment; hence, the term
G in the introductory equation above is equal to the loss from water to
sediment:

Cwater
cont
Cwater
cont
2Cwater
cont
Csed
cont
= v +D b
t x x 2
t

Since Csed usually has units of Mc/Msed and Cw usually has units of Mc/L3w,
the proportionalities include parameters such as (L3w/ L3REV) and b
(Msed/L3REV) to get the concentrations into equivalent units (Mc/L3REV).
Reversible Linear Reactions - Derivation of R
Now recall that under conditions of equilibrium sorption:

cont
Csed = K d Cwater
cont

Csed
cont
Cwater
cont
And so: = Kd
t t

Cwater
cont
Cwater
cont
2 Cwater
cont
Cwater
cont
So: = v +D Kd b
t x x 2
t

b Cwater Cwater 2 Cwater

cont cont cont
Or: 1 + Kd = v +D
t x x 2

Note that this equation is equivalent to equation 4 except for the term
preceding the L.H.S.. This term is a factor which accounts for equilibrium
sorption of the contaminant to the sediment, as quantified by Kd.
Influence of reversible linear adsorption on breakthrough
Thus the retardation factor represents the average velocity of
water relative to the average velocity of the contaminant.
water water cont cont
v ave v ave L 1 travel time water travel time water
R = cont = cont
= water
= water
v water L v water travel timeave 1 travel timeave

Hence, a contaminant with an R of 40, will travel 40 times

slower than water. So if it takes 1 year for groundwater to travel
from point A to point B, the contaminant will take 40 years to
travel that distance, because of sorption.
On a breakthrough curve, retardation looks like this:

Cin

C R=1 R = 3.8

1 year 3.8 year

time
 Dispersion Sorption
breakthrough curve breakthrough curve
conservative sorbing
1.0 1.0
dispersion
C/C0 C/C0

0 0
time time
top view field top view field

Year 1

Year 2

Year 3
Influence of reversible linear adsorption on breakthrough

So how does R affect the Ogata-Banks solution?

Cwater
cont
Cwater
cont
2Cwater
cont
R = v +D
t x x 2

Cwater
cont
v Cwater
cont
D 2Cwater
cont
= +
t R x R x 2
It doesnt affect the math (the solution) other than dividing
the values of v and D by R!
Irreversible reactions transport distance
In a system with advection and dispersion, this loss is subtracted from the
aqueous concentration:

Cwater
cont
Cwater
cont
2Cwater
cont
= v +D kCwcont
t x x 2

Once steady state breakthrough is achieved dispersion is negligible and the transient
term is zero
Cwater
cont
Cwater
cont
1
= v kCwcont
t x
Removing these two terms yields:
Cwater
cont
v = kCwcont Low k
x C/C0
Re-arranging:
Cwcont k
cont
= x
C v
w
high k
Integrating:
0
C cont k
Ln wcont = x x
Cw, 0 v
Irreversible reactions Influence on breakthrough
Breakthrough at L
Cin
k=0
No retardation of
breakthrough C k>0

Breakthrough
concentration a
1 year time
function of k and
distance Breakthrough at 2L
Cin
k=0

C
k>0

2 year
time
 C Tracer C Partitioning
1.0 = =
t t
0.9 C 2C C
C 2C
v +D v +D K b
0.8 x x 2 x x 2
d
t
0.7 b
1 + Kd = R
0.6
C/C0

0.5
0.4 Filtration

0.3 C C 2C
= v +D kfC
0.2 t x x 2

C kf
= exp( L)
0.1 Co v
0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Pore Volumes
Experimental Procedures
Field Experiments
Inject particles into the ground
Pros: Most realistic
Cons: Heterogeneity in subsurface makes quantitative predictions
difficult/impossible
Experimental Procedures
Field Experiments
Inject particles into the ground Co

Pros: Most realistic

Cons: Heterogeneity in subsurface makes quantitative
predictions difficult/impossible
Column Experiments
Packed column of soil/sand/glass beads
Pros: Control over material packed in column
Cons: Black-box. Cant see whats happening inside

C
Experimental Procedures
Field Experiments
Inject particles into the ground
Pros: Most realistic
Cons: Heterogeneity in subsurface makes quantitative predictions
difficult/impossible
Column Experiments
Packed column of soil/sand/glass beads
Pros: Control over material packed in column
Cons: Black-box. Cant see whats happening inside
Micromodels
Porous Media:
Transparent micro-column packed with spherical collectors
Pros: Allow observation of particles interacting with collectors
Cons: Microscope can only focus on one plane, hard to quantify attachment
Experimental Procedures
Field Experiments
Inject particles into the ground
Pros: Most realistic
Cons: Heterogeneity in subsurface makes quantitative predictions difficult/impossible
Column Experiments
Packed column of soil/sand/glass beads
Pros: Control over material packed in column
Cons: Black-box. Cant see whats happening inside
Micromodels
Porous Media
Transparent micro-column packed with spherical collectors
Pros: Allow observation of particles interacting with collectors
Cons: Microscope can only focus on one plane, hard to quantify attachment
Impinging Jets
Jet of colloid-laden solution impinges on a flat collector (glass slide)
Pros: single focal plane, attachment easily quantified
Cons: Hard to compare to porous media, lacks a rear flow stagnation zone.
Column Experiments
Breakthrough curve: measure concentration in effluent, compare to inlet
concentration versus time.
Retention profile: dissect column and measure concentration versus distance.
This provides a snapshot in time.

Tong et al. 2005a

From pore scale to field scale
Nc/L depends on collector geometry
For Happel sphere-in-shell:
3(1)1/3
=
2

Johnson and Hilpert 2013