SSC 107, Fall 2002 – Chapter 6 Page 6-1

Chapter 6 - Solute Transport

• fertilizer movement

• leaching of salt (reclamation)

• pollutant movement

Transport depends on

• H2O flow velocity

• Water content

• Soil characteristics

• Solute species

• Solute reactions

Examples

• Solute in soil originally

• Applied as a pulse by fertilizer application or contaminant spill

• Applied continuously with irrigation water

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SSC 107, Fall 2002 – Chapter 6 Page 6-2

Miscible Displacement

displacing Mixing displaced

zone

Definition: Displacing solution is miscible (mixes) with displaced solution

• Mixing occurs at boundary
• Mixing due to diffusion and dispersion
• Dispersion due to mass flow of H2O

For No Mixing at Boundary (Immiscible)

1.0

C = Co
C=0 C/Co

0.0
1 2
Pore volume

Piston Displacement

CT (or C)- the concentration of the material of interest as it exists from the
column
Co - the initial concentration of the material of interest that enters the column

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 SSC 107, Fall 2002 – Chapter 6 Page 6-3

Volume Effluent
# of Pore Volumes =
Total Volume Solution in Media

For soil, total volume of solution in media (Vl) is

Vl = θv V

Water content (cm3/cm3) Volume of Soil

Solute is the material we are trying to measure.

Solutes in soil initially Pulse of solute

1 1

C/C0 C/C0

0 0
Pore Volume Pore Volume

Solute applied continuously Effect of flow velocity

1 1
Saturated

C/C0
C/C0
0.04 cm/h

1.9 cm/h

0 0
1.0 1.0
Pore Volume Pore Volume

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 SSC 107, Fall 2002 – Chapter 6 Page 6-4

Effect of Water Content

1

C/C0 θ=0.27

θ=0.33

θ=0.36

0
1.0
Pore Volume

• Desaturation eliminates larger flow channels (larger pores) and increases the
proportion of the volume of water that does not readily move. These almost
stagnant zones (soil micropores) act as sinks to ionic diffusion

• Desaturating the soil causes an incomplete displacement of the initial solution by the
solute, thus a more rapid appearance of solute is observed.

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 SSC 107, Fall 2002 – Chapter 6 Page 6-5

Effect of soil texture (Pore size distribution)

Yolo
C/C0 loam

Oakley
sand
0
Pore volume

- Wider pore size distribution allows for more relatively stagnant

zones in loam.

Effect of solute
1

Tritium
C/C0
Cloride

0
Volume of effluent

Cl- excluded by surface of the colloid (assumes the soil has a high
C.E.C.)

Tritium (radioactive water) has some proton exchange.

☺For a soil with a significant CEC, where would you expect the breakthrough
curves for cations to appear? How about pesticides?

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 SSC 107, Fall 2002 – Chapter 6 Page 6-6

Capillary Model for Solute Transport

0.1 1

r 0 C=C0 C=0 C/C0

0.1 0
Distance, x x

Velocity inside tube at any radius, r, is given by equation below. The total radius of the
tube is a.

 2

v = 2 vo  1 - r 2 
 a 

average
velocity

Mass flow inside tube

 2

flux Jx = 2 vo  1 - r 2  C
 a 

A “cube” of soil depicting solute moving through the cube

Storage of solute inside cube = flux out minus the flux in

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SSC 107, Fall 2002 – Chapter 6 Page 6-7

Continuity Equation for capillary tube

∂C  2
 ∂C
= - 2 vo  1 - r 2 
∂t  a  ∂x

C/C0 Velocity
Dispersion

0
1

Pore Volume

Problems with the capillary model

1. Soil not capillary tubes
2. Longitudinal diffusion occurs
3. Average pore size - Won’t work because pores irregular and
diffusion complicated

Convection-Dispersion Model

Bulk flow (mass flow) flux of dissolved solute

Jlc =Jw Cl
Where Jlc is bulk flow flux
Jw is the water flux
Cl is the dissolved solute concentration

Hydrodynamic dispersion flux

∂C l
Jlh = - Dlh
∂z

where Jlh is the hydrodynamic dispersion flux

Dlh is the hydrodynamic dispersion coefficent
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SSC 107, Fall 2002 – Chapter 6 Page 6-8

This equation looks like Fick's Law for diffusion.

Liquid diffusion flux

∂C l
Jld = - Dsl
∂z

where Jld is the liquid diffusion flux

s
Dl is the soil liquid diffusion coefficient

This is Fick's Law for solute diffusion in soil.

Total flux of dissolved solute

J l = J lc + J lh + Jld
∂C ∂C l
= J w Cl - Dlh l - Dsl
∂z ∂z
Or, by combining the last two terms

∂C l
Jl = - De + J w Cl
∂z
where De = Dlh + Dsl and

De is the effective diffusion-dispersion coefficient.

Continuity Equation (Conservation of mass)

1. For nonsorbing, nonreactive solutes

∂C l ∂J
θv =- l
∂t ∂z

∂ Cl ∂  ∂ Cl  ∂
θv = De - [J w Cl]
∂ t ∂ z  ∂ z  ∂ z

If De and J w are constant with Z

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SSC 107, Fall 2002 – Chapter 6 Page 6-9

∂ Cl 2
∂
= D ∂ C2l - V Cl
∂t ∂z ∂z

where D = De / θv and V = J w / θv

V is an average pore water velocity since pores not all the same size.

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SSC 107, Fall 2002 – Chapter 6 Page 6-10

Dispersion as affected by pore-water velocity

-It has been shown from many experiments that D (or De) increases as the pore-water
velocity increases.

D (or De)

s
Dl

0
v
s
De = Dlh + Dl

-Since Dsl is not expected to change with velocity, Dlh is the term changing with
velocity.

-This extra spreading due to hydrodynamic dispersion is due to complicated flow paths
around soil particles, to differences in water velocity within single pores, and to
differences in water velocity in adjacent pores.

2. Equation for adsorbing chemicals

ρb ∂ Ca ∂ Cl 2
∂
+ = D ∂ C2l - V Cl
θv ∂ t ∂t ∂z ∂z

where Ca is adsorbed concentration.

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SSC 107, Fall 2002 – Chapter 6 Page 6-11

Ca is often given by a linear adsorption isotherm

Ca = Kd Cl

where Kd is the distribution or partition coefficient.

If the linear isotherm is substituted into the transport equation above, the following
equation is obtained:

where R = 1 + ρb Kd/θv is the retardation factor. Dividing the above equation by R

∂ Cl 2
∂
R = D ∂ C2l - V Cl
∂t ∂z ∂z

gives

∂ Cl 2
∂
= DR ∂ C2l - VR Cl
∂t ∂z ∂z

where DR = D/R and VR = V/R are the retarded dispersion coefficient and retarded
velocity, respectively.

3. Equation for reactive chemicals

If the chemical being transported through soil is reactive meaning that it "breaks
down", either chemically or biologically, to some other chemicals, the following
equation must be used

∂ Cl 2
∂
θv = De ∂ C2l - J w Cl - S
∂t ∂z ∂z

where S is some kind of sink term. This term may be a kinetic-type relationship such as
zero order, first order, Michaelis-Menton, Monod, etc. For an example of first-order
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SSC 107, Fall 2002 – Chapter 6 Page 6-12

decay, see the text (Jury et al., 1991).

☺For chemicals that are biodegraded, how would biodegradation affect the shape
of the breakthrough curve for that chemical?

The following figures show experimental apparatus and data from experiments with
different porous materials, flow rates, and chemicals:

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SSC 107, Fall 2002 – Chapter 6 Page 6-13

From Biggar and Nielsen (1962).

Displacement of water by a chloride solution in a 10-cm column of glass beads under

steady saturated and unsaturated conditions. From Krupp and Elrick (1968).

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SSC 107, Fall 2002 – Chapter 6 Page 6-14

From Kutilek and Nielsen (1994)

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SSC 107, Fall 2002 – Chapter 6 Page 6-15

From Biggar and Nielsen (1962).

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SSC 107, Fall 2002 – Chapter 6 Page 6-16

From Biggar and Nielsen (1962).

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SSC 107, Fall 2002 – Chapter 6 Page 6-17

From Rolston et al. (1979).

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SSC 107, Fall 2002 – Chapter 6 Page 6-18

From Castro and Rolston (1977)

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SSC 107, Fall 2002 – Chapter 6 Page 6-19

From Kutilek and Nielsen (1994)

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SSC 107, Fall 2002 – Chapter 6 Page 6-20

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SSC 107, Fall 2002 – Chapter 6 Page 6-21

Exclusion or
immobile water

Diffusion
and
dispersion

From Kutilek and Nielsen (1994).

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SSC 107, Fall 2002 – Chapter 6 Page 6-22

From Stephens (1995).

Apparatus for sampling the soil solution

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SSC 107, Fall 2002 – Chapter 6 Page 6-23

Soil solution sampling porous cup, pressure-vacuum samplers showing: (A) installation
in a backfilled borehole, (B) installation in a backfilled trench, and (C) sampler
construction. (Courtesy of Soilmoisture Equipment Corp.)

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