V.

Solute Transport
Chap V. Solute Transport in Soils
5.1. Introduction
Soil water carries its solute load in its convective stream, leaving some
of it behind to the extent that the component salts are absorbed, taken
up by plants, or precipitated whenever their concentration exceeds their
solubility (e.g. at the soil surface during evaporation).
Transport of solutes in porous materials such as soils is important in
understanding problems of chemical residue, salinity, availability of
solutes for plant uptake, leaching or redistribution within the vadose
zone to groundwater, runoff to surface water, and seepage from various
storage and waste disposal systems.
Solute transport in soil depends on H
2
O flow velocity, water content, soil
characteristics, solute species (mobile and immobile), solute reaction,
etc.
Transport of solutes in soil occurs by two physical processes; namely
Diffusion
Convective flow mass flow
5.2. Diffusion
Diffusion is the movement of ions or molecules from areas of higher to
areas of lower concentration. This is generally proportional to the
concentration gradient, the cross sectional area available for diffusion,
and the time during which the transport process occurred.
Page V.1: AgEn 311: Soil Physics
V. Solute Transport
Ficks First Law
The net amount of solute crossing a plane of unit area in unit time is
known as the flux density and is given by the empirical relation known
as Ficks first law. In one dimensional form, Ficks first law for a steady
state transport is given as:-
J = -D

C
Where J is the solute flux density ) (
2
s m kg , D is the molecular
diffusion coefficient ( ) s m /
2
, C- is the concentration of solute (kg/m
3
), Z
is the distance is (m). The minus sign arises because solute movement
occurs from areas of higher to areas of lower concentration, and it
serves to make J positive in the direction of positive z)

Solid phase Diffusion Distance
coefficient (m
2
/s) moved (m/d)
Gaseous 2 x 10
-5
1.86
Solution 2x10
-9
0.0186
Soil (whole)* 2x10
-11
0.00186
Solid (adsorbed) 2x10
-13
0.000186
*Diffusion in the three phases of soil
Q5.1
Assume that a solute with a diffusion coefficient of 2x10
-10
m
2
/s in soil is
diffusing under steady state conditions into zone originally devoid of the
solute. If the concentration of the solute is 25 mg/g of the soil and the
bulk density is 1.3 g/cm
3,
calculate the following using Ficks first law.
a. The flux density in the Z direction at a distance of 0.1 m, and
b. The amount of the solute in 1 hectare that diffused across this
boundary in 1 month.
Page V.2: AgEn 311: Soil Physics
V. Solute Transport
Ficks Second Law
For transient state conditions, the concentration of mass equation has
to be satisfied. In one dimension and without generation and
consumption, this equation is
t
C

= -
Z
J

which implies that the rate of change of solute concentration equals the
net rate of flow over the boundary. Combining equation (2) and (4)
yields the transient form of the diffusion equation:

,
_

z
C
D
z t
C
Which is known as Ficks Second Law. If the solute diffusion coefficient is
independent of solute concentration and depth, equation above
simplifies to
2
2
z
C
D
t
C

This has been solved analytically and numerically for several initial and
boundary conditions.
Analytical Solution and Application
One analytical solution is given for situation:-
when a solute is uniformly broadcast on the soil surface in
quantities high enough to cause saturation in solution,
if the initial concentration of solute in the profile is negligible, and
if only diffusion transport occurs.
if there is no root water uptake by plant roots the solute will
diffuse downward into the soil profile.
The solute concentration distribution C(z, t) at some depth z and time t
after application can be estimated from
C(z, t) = C
o
erfc
1
]
1

5 . 0
) ( 2 Dt
z
Page V.3: AgEn 311: Soil Physics
V. Solute Transport
Where C
o
is the initial concentration, which remains constant and erfc is
the complementary error function which is related to the normal, or
Gaussian distribution function.
Solution the above equation for two values of D and t are:-
Diffusion from a constant source in 1 day
Q5.2
Assume that the diffusion coefficient of a given solute in soil was 1

10
-9
m
2
s
-1
. Find the value of the relative concentration. C/C
o
at a depth of 5
m after 100 years of diffusion only.
5.3. Convection
If water in the soil is also moving the solute is swept along by the
physical transport process known as mass flow (advection or convective
flow). The simplest way to visualize convection is called piston of low or
simple convection.
Page V.4: AgEn 311: Soil Physics
1.0
0
100
z (mm)
R
e
l
a
t
i
v
e

c
o
n
c
e
n
t
r
a
t
i
o
n
V. Solute Transport
Steady state convection
Consider a column of soil with pure water uniformly moving through it
`
Assume that we quickly replace the water at the intake end of the
column with a solution containing a solute at some known concentration,
C
o
. In piston flow, the solute will travel through the column, at the some
rate as the flow of water and will not spread. At the outflow end of the
column, the concentration of the solute is zero until the front appears at
which time the concentration of the solute becomes the same as that at
the inflow end of the column.
The solute flow rate in the column can be described by the product of
the macroscopic flow rate of water (i.e. the Darcy flux density) and the
concentration of the solute in that water. In the Z dimension, this solute
flow rate is determined by
l z z
C q J
Where
J
z
is the solute flux density (kg, m
-2
S
-1
) of soil in the Z direction (m)
q
z
is the macroscopic water flow rate per unit area perpendicular to the
Z direction (m/s), and
C
l
- is the concentration of the solute in that water (kg/m
3
)
The flux density of soil water is calculated by the Darcy equation for
steady state flow of water.
Page V.5: AgEn 311: Soil Physics
V. Solute Transport
Since in soil
v q
v

, we can also write
l v z
C v J
. Where v is the average
water velocity in the soil pores in the Z direction (m/s) and
v

is the
average volumetric soil water content (m
3
water per m
3
- soil)
Q5.3
If the soil water flux density is 0.045 cm/d downward, the soil water
content is 0.35 m
3
.m
-3
and the soil solution concentration of nitrate N is
3 l mg calculate the pore water velocity and the amount of nitrate N
moved by convective flow per unit area below the plant root zone in 1
day.
Transient state convection
Combining equations

J
t
c
, and
l z
C v J

we obtain the one dimensional conservation equation for convective
flow.
( )
z
C v
t
c
l v

Solution of this gives a sharp concentration front in which on the
advancing side of the front, the solute concentration is equal to the
inflow C
o
and on the other side it is equal to the initial concentration C
i
.
This is known as piston (or plug) flow where all of the resident soil water
is replaced by the invading solute front. The sharp interface that results
from piston flow is shown
Page V.6: AgEn 311: Soil Physics
(
R
e
l
a
t
i
v
e

c
o
n
c
e
n
t
r
a
t
i
o
n
)
1
0
o
C C
Time
V. Solute Transport
It should be emphasized that piston flow very seldom, if ever occurs in
field soils, but it is a useful first approximation of the potential
movement of solutes. Non-uniform flow mechanism such as
hydrodynamic dispersion, preferential flow, and fingering lead to solute
concentration distributions that differ significantly from those predicted
by piston flow.
Fingering is the preferential movement of water in soil along a vertically
elongated path. These heterogeneous concentration distributions are
usually attributed to the influence of non-homogenous of soil properties
such as soil structure and biological channels resulting in water and
solute flowing more rapidly in large pores than in small pores.
Mechanical Dispersion
As a solute moves through the soil profile, it mixes with the soil solution,
which has a different chemical composition. Initially, there is a sharp
boundary or interface between the solute concentration of the new and
old solutions. Eventually, a transition zone develops between the two
solutions where the solute concentration varies.
Assuming no interaction between the solute and soil surface (i.e no
sorption), the solute concentration curve varies with time and has the
shape of the S curve.
The tendency for solute molecules to become more diffuse with time
when water is moving is known as mechanical dispersion. Dispersion
occurs when a transition zone develops between two solutions of
differing chemical compositions. The change in width of the front is due
to both diffusion and mechanical dispersion. However, it is not
generally possible to separate the effects of the two processes.
Page V.7: AgEn 311: Soil Physics
V. Solute Transport
Hydrodynamic dispersion can be visualized as occurring in soil when the
water is moving. Its velocity distribution is not uniform because of three
boundary effects. Causes contributing to hydrodynamic dispersion of
solutes are:-
a. Zero velocity at the soil particle surface (capillary model).
Velocity inside the tube at any radius (r) is given by the equation
below

,
_

a
r
v v
o
2
1 2
b. Variation in pore size
Causing different average flow
velocity between the pores of the
soil
c. Influence of microscopic flow direction
The mixing or dispersion that occurs along the direction of the flow path
is called longitudinal dispersion. The dispersion in directions normal
to the flow path is called transverse dispersion. Both of these
mechanical dispersion coefficients are the result of the product of the
linear velocity of the fluid in the principal direction of flow and a
property of the soil called the dispersivity.
The mathematical equation for the flux density of solutes by
hydrodynamic dispersion is

z
C
D J
l
lh h

Page V.8: AgEn 311: Soil Physics
V. Solute Transport
Where
lh
D
is the hydrodynamic dispersion coefficient (m
2
/s). The
magnitude of the dispersion coefficient depends on the pore water
velocity and the solute diffusion coefficient. Since the effects of diffusion
and dispersion on the concentration distribution are similar, they are
often combined even though the mechanisms of transport are different.
Miscible Displacement and Breakthrough curves
Miscible refers to the displacement of one fluid by another miscible fluid
in soil.
Steady- state flow conditions when the initial soil solution with a
solute concentration of C
i
, is invaded and eventually displaced by a
second miscible solution with solute concentration C
o
.
No mixing of the two solutions should occur at the ends of the column
and side walls. Samples of the effluent are collected and analyzed for
the solute without disturbing the flow.
Let the volume of the soil column occupied by the resident solution
be V
o
(m
3
) and the steady state rate of inflow and outflow of the
solution be
t Q/
(m
3
/s). The initial solute concentration, C
1
, is suddenly
displaced by an incoming solute concentration solution, C
o
. The
fraction of this incoming solute in the effluent at time (t) will be
Ci Co
Ci C

or for an initial concentration (C

i
) of zero, simply
Co
C
.
Plot of the relative concentration ,
Co
C
at a fixed location (usually the
outlet of the column) versus pores volume of effluent,
o
V Q
are called
Breakthrough curves (BTCs).
Pore volume[-] is defined as the ratio of the column effluent volume
to the total pore water volume in column.
Page V.9: AgEn 311: Soil Physics
V. Solute Transport
The parameter t is the time since the dissolved solute was introduced
to the effluent.
The BTCs describe the transport behavior of the solute in the soil and
provide information on interactions between the soil matrix and
solute.
Example of breakthrough curves for miscible displacement.
o
C C
is the relative concentration of the solute measured in the
effluent, and pore volume is the ratio of the volume of effluent to the
volume of fluid in the soil column. Curve number 1 is for no
dispersion, curve 2 is for dispersion with no sorption, and curve 3 is
dispersion with sorption.
If there is no dispersion and the dissolved solute is conservative
(i.e. no sorption or microbial or chemical transformation), at 1 pore
volume the effluent break though relative concentration will
instantaneously reach 1.0, being zero until 1 pore volume is
displaced from the column.
Page V.10: AgEn 311: Soil Physics
3
2
1
o
C C
Pore Volume
V. Solute Transport
Page V.11: AgEn 311: Soil Physics
V. Solute Transport
Derivation of the solute Transport Equation
The derivation (in complete form) of the equations used for the
prediction of solute transport in soils will be derived first by summing
the steady state flow processes in the three phases. Then, with the aid
of the law of conservation of mass, the transient state processes will
be accounted for.
Steady state solute transport
Under steady- state conditions, the flux density of solutes in soil is the
sum of the flux densities in the three phases of soil. Mathematically, this
can be written as
a g l s
J J J J + +
Where J
s
is the total solute flux density in soil, J
l
, is the flux density in the
liquid phase, J
g
is the flux density in the gas phase and J
a
flux density in
the solid/adsorbed phase.
Values of J
a
are usually considered negligible compared to the overall
macroscopic transport process of solutes and often ignored when long
distance transport is considered. For solute transport in the soil air gas
phases the diffusion is the primary transport mechanism. We use Ficks
first law to write
z
C
D f J
g
g g g

Where f
a
is the aeration porosity (m
3
/m
3
), D
g
is the molecular diffusion
coefficient in the gas phase (m/s), and C
g
is the concentration of the
solute in the gas phase (kg /m
3
of soil air.
In the liquid phase, both diffusion and concoctive flow transport
processes operate. The convective flux density, J
l
, can be represented by
Page V.12: AgEn 311: Soil Physics
V. Solute Transport
l
l lc ld v l v h
C
J J J v C D v
z


+

Often, it is difficult to separate diffusion from dispersion, and these

terms are combined and collectively called diffusion- dispersion (and
taken as D).
The total solute flux density in the liquid phase, J
l
, is the sum of the
diffusion and convective dispersion flux densities.
l v
l
v l
C v
z
C
D J +

Where D is the diffusion- dispersion coefficient of the solute. The first
term on the right hand side is the contribution of dispersion (molecular
diffusion and mechanical dispersion), and the second term is the
contribution of convective flow.
Neglecting the adsorbed (J
a
) component, the steady state solute flux
density in soil, J
s
, is written as
z
C
D f C v
z
C
D J
g
g a l v v s

1
This combines the solute flux densities in both liquid and gaseous
phases of soil.
The general form of the mass balance equation for one dimensional
solute flow in the same direction as water and without generation and
consumption can be represented as
( )
z
J
t
C
s l v

Note that
C C
l v

and J
s
is expressed on a soil basis.
Page V.13: AgEn 311: Soil Physics
V. Solute Transport
For a conservative solute with negligible diffusion in the gaseous phase,
combining the previous two equations gives the convective
dispersion equation (CDE):
v l
v v l
C C
D v C
t z z

1

1

]
For steady state transport of water in a homogenous soil with uniform
soil water content, the above equation can be simplified to
z
C
v
z
C
D
t
C

2
2
Which is the general transport equation for transient, isothermal flow of
solutes in soil. The equation is second order linear differential equation
also called parabolic differential equation. For solutes such as pesticides
and fertilizers, consumption and generation are significant terms in the
conservation equation. Under these conditions,
( )
r
z
J
t
C
s l v
t

The quantity r is composed of both source and sinks terms and has the
same units as t C . Examples of sources and sinks include:-
Release of ions from non-exchangeable to exchangeable form
Release or fixation (sorption) of solutes by soil surfaces
Degradation of organic solutes by chemical or microbial action
Uptake by plants
Generation by microbial and enzymatic process.
The parameter r is a collective term that combines one or more
generation and consumption rate processes. Assuming loss of solutes by
sorption by soil surfaces only, r can be represented by
t
S
r
b

Where
b

is the soil bulk density, and S is the amount of solute in the

solid or adsorbed phase (kg solute/ kg of soil). Normally the symbol S is
used in soil physics literature instead of C
a
.
Page V.14: AgEn 311: Soil Physics
V. Solute Transport
For a given unit volume of soil, the total concentration of a nonvolatile
solute (kg m
-3
) is represented by the sum of the amounts retained by soil
surfaces and that present in the solution phase. The total resident solute
concentration in soil is defined as the sum of the volume weighted
concentrations in the three phases and is
g a l v a b
C f C C C + +
The revised form of this equation is
l v b
C S C +
Differentiating with respect to t, assuming that
b

is constant with t, and

substituting the result into
z
C
v
z
C
D
t
C
l l l

2
2
Gives the following form of CDE:
( )
z
C
v
z
C
D
t
S
t
C
l
v
l
v b
l v

2
2
Using the chain rule, collecting t C terms and assuming that
v

does
not change with z or t, we define
l v
b
dC
dS
R +

1
=1
b
d
K

+
For no interaction between the solute and the soil K
d
= 0 and R=1. Here
R is called the retardation coefficient.
For organic and inorganic cations and neutral molecules, R will be
greater than 1. However, if there is no sorption of the solute by soil
surfaces, then the term
l
dC dS
is zero and R becomes 1. This assumption
is often made of anionic and neutral tracers such as chloride, bromide,
and tritium. However, if there is ion exclusion, R may be less than 1.
Finally, the CDE that accounts for sorption of a conservative solute by
soil surfaces is written as
Page V.15: AgEn 311: Soil Physics
V. Solute Transport
z
C
v
z
C
D
t
C
R
l

1
2
2
1
Many organic and inorganic solutes undergo decomposition by biological
and chemical processes. The loss of the solute by decomposition is
frequently represented by
c k r
Where k is the first order decay constant (s
-1
). Substitution of above
equation in to equation
z
C
v
z
C
D
t
C
R
l

1
2
2
1
results in the CDE for a solute that both is sorbet by soil surface and
undergoes first order decomposition:
l v
l
C k
z
C
v
z
C
D
t
C
R

1
2
2
1
Furthermore, we define the apparent diffusion dispersion coefficient as
De =
R
D
And the apparent pore water velocity as
R v v
e

and the apparent
degradation rate coefficient as R k B .
Finally, the solute CDE becomes
l v e
l
e
C B
z
C
v
z
C
D
t
C

1
2
2
1
This transient state equation connects the one- dimensional flow of soil
water in homogenous soil with the spatial and temporal transport of
solutes as modified by sorption and degradation.
Page V.16: AgEn 311: Soil Physics
V. Solute Transport
Q5.5 Convection under steady state conditions
Calculate the amount of time required to transport the anion NO
3
from
the bottom of the root-zone of a pasture to groundwater that is 60 m
below if the average soil water content is 0.25 m
3
m
-3
and the average
drainage rate is 0.30 m/y and where no diffusion and dispersion occur.
Use the piston flow model for the calculations.
Q5.6
A soluble pollutant was inadvertently spilled on the ground. Suppose
that it is non degradable, nonvolatile and not taken up by pants, not
adsorbed by the soil, and not immobilized by any other mechanism. If
the annual rainfall 1500 mm, the annual evapotranspiration is 1250 mm,
the water tale is 20 m deep, and the so called unsaturated zone
underlying the soil has a constant volumetric wetness of 25%, estimate
the residence time in the unsaturated zone and the time required for
the pollutant to reach the groundwater
Q4.6
Calculate the amount of time required to transport a pesticide from the
bottom of the root zone to the groundwater 60 m below if the average
soil water content is 0.25 m
3
m
-3
and the average drainage rate is 0.3 m
per year. Assume that
l
C S
is 2 cm
3
/g and the bulk density is 1.5 Mg
m
-3
. Use the piston flow model with retardation for the calculations.
This examples show the influence of sorption on retarding of solutes in
soil. The adsorbing pesticide had a breakthrough time that was R times
longer than that of the non adsorbing anion N0
3
.
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V. Solute Transport
Q4.7
Show the influence of depth to the groundwater in the previous example
for L = 10, 20, 30 and 60 m.
Solution
For NO
3
and the pesticide, the predicted breakthrough times are
Break Through Time (y)
L(m) Nitrate Pesticide
10 8.33 108.3
20 16.67 216.7
30 25.00 325.0
60 50.00 650.0
This shows that the breakthrough time increases with distance to the
water table.
Page V.18: AgEn 311: Soil Physics