EAS 44600 Groundwater Hydrology

Lecture 16: Solute Transport in Saturated Media

Dr. Pengfei Zhang
Introduction
In this lecture we will discuss the transport of dissolved solutes in groundwater, the so-called
mass transport or solute transport. The transport of colloidal-size particles in groundwater is
much more complicated and beyond the scope of this course.
There are two basic processes controlling the transport of solutes in porous media: diffusion and
advection. Diffusion is the process by which a solute moves from areas of higher chemical
potentials to areas of lower chemical potentials. This process is also known as molecular
diffusion. Advection is the process by which dissolved solutes are carried along with the
flowing groundwater.
Diffusion
For a one-dimensional system where the concentration of a solute (C) changes with time, Ficks
second law applies:
C
2C
= Dd
(16-1)
t
x 2
where C/t is the change in concentration over time, Dd is the diffusion coefficient, and 2C/x2
is the second derivative of concentration with respect to transport distance. Values of Dd for ions
in water at 25 C can be found in Table 16-1.
Table 16-1. Diffusion coefficients in water at 25 C.
Cations
H+
Na+
K+
Rb+
Cs+
Mg2+
Ca2+
Sr2+
Ba2+
Ra2+
Mn2+
Fe2+
Cr3+
Fe3+

-9

Anions
OHFClBrHSHCO3SO42CO32-

9.3110 m /sec
1.3310-9 m2/sec
1.9610-9 m2/sec
2.0610-9 m2/sec
2.0710-9 m2/sec
7.0510-10 m2/sec
7.9310-10 m2/sec
7.9410-10 m2/sec
8.4810-10 m2/sec
8.8910-10 m2/sec
6.8810-10 m2/sec
7.1910-10 m2/sec
5.9410-10 m2/sec
6.0710-10 m2/sec

16-1

5.2710-9 m2/sec
1.4610-9 m2/sec
2.0310-9 m2/sec
2.0110-9 m2/sec
1.7310-9 m2/sec
1.1810-9 m2/sec
1.0710-9 m2/sec
9.5510-10 m2/sec

In porous media, diffusion cannot proceed as fast as it can in water because the solute bounces
around mineral grains as it travels. To account for this, an effective diffusion coefficient, D*, is
used:
D * = Dd
(16-2)
where is a coefficient related to the tortuosity of the flow paths. The value of is always less
than 1, and typically ranges from 0.5 to 0.01 for laboratory studies using geologic materials.
Advection
Recall that the average linear velocity (v) of the flowing groundwater can be determined from
Darcys law:
K dh
v=
(16-3)
ne dl
where ne is the effective porosity, the porosity available for fluid flow.
Advecting solutes are traveling at the same rate as the average linear velocity of the groundwater
if the solutes are not subject to any sort of reactions with the porous media.
The one-dimensional advective transport equation is

C
C
= v
t
x

(16-4)

Mechanical Dispersion
Groundwater molecules are moving at different rates, some are faster than the average linear
velocity while some are slower. There are three causes for this phenomenon: friction on pore
walls, variations in pore sizes, and variations in path length (Figure 16-1). As groundwater
moves through the pores, it will move faster at the center of the pore than along the walls due to
friction. In cases where different size pores exist, groundwater will move through larger pores
faster. Groundwater molecules have tortuous flow paths and some will travel longer pathways
than others.
Because the invading solute-containing water is not all moving at the same rate, mixing occurs
along the flow path. This mixing is termed mechanical dispersion. The mixing that occurs
along the direction of fluid flow is termed longitudinal dispersion, whereas the mixing that
occurs normal to the direction of fluid flow is termed transverse dispersion. Transverse
dispersion is thought to be the result of the split of flow paths to the side (Figure 16-2).
In a one-dimensional system, mechanical dispersion is equal to the product of the average linear
velocity (v) and the longitudinal dispersivity (L):
Mechanical dispersion = L v

16-2

(16-5)

Figure 16-1. Factors causing pore-scale longitudinal dispersion (Fetter).

Figure 16-2. Flow paths in a porous medium that cause transverse dispersion (Fetter).
Hydrodynamic Dispersion
Since molecular diffusion cannot be separated from mechanical dispersion in flowing
groundwater, the two are combined into a parameter called hydrodynamic dispersion
coefficient, D:

D = Lv + D*

(16-6)

16-3

where L is the longitudinal dispersivity, v is the average linear velocity, and D* is the effective
diffusion coefficient.
Due to hydrodynamic dispersion, the concentration of a solute will decrease over distance.
Generally speaking, the solute will spread more in the direction of groundwater flow than in the
direction normal to the groundwater flow, because longitudinal dispersivity is typically 10 times
higher than transverse dispersivity. In fact, most of the solute plumes or slugs are long and
skinny (Figure 16-3).

Figure 16-3. The development of a contamination plume from a continuous point source (A) and
the travel of a contaminant slug from a one-time point source (B). Density of dots indicates
solute concentration.
The transport of a conservative solute in a one-dimensional system can be described by the
advection-dispersion equation

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

(16-7)

where C/t is the change in concentration over time, the first term on the right-hand side
represents advection, and the second term represents hydrodynamic dispersion.
The advection-dispersion equation may be solved analytically or numerically under different
initial and boundary conditions. Due to the complexity, we will not get into the details of the
solutions; instead, we will learn how to use software to obtain solutions.

16-4