SOLUTE TRANSPORT

Advection
• Advection is mass transport due simply to the
flow of the water in which the mass is carried.
• The direction and rate of transport coincide
with that of the groundwater flow.
 Diffusion
• Diffusion is the process of mixing that occurs
as a result of concentration gradients in
porous media.
• Diffusion can occur when there is no hydraulic
gradient driving flow and the pore water is
static.
• Diffusion in groundwater systems is a very
slow process.
 Dispersion
• Dispersion is the process of mechanical mixing
that takes place in porous media as a result of
the movement of fluids through the pore
space.
• Hydrodynamic dispersion is a term used to
include both diffusion and dispersion.
Pure Advection
Advection in Stream Tube
 Linear Advective Velocity

From Darcy’s Law:

v = q / ne = - (K / ne).dh/dx

where ne is the effective (or connected)

porosity
 Fractured Rocks and Clays
• In fractured rocks, the effective porosity (ne)
can be very small implying relatively high
advective velocities.
• In clays and shales, effective porosity can also
be very low and high advective velocities
might be expected but there are other factors
at work.
 Deviations from Advective Velocity
• Electrical charges on clay mineral surfaces can
force anions to the centre of pores where
velocities are highest.
• Anions can then travel faster than the advective
velocity.
• Cations are attracted by the clay mineral surface
charge and can be retarded (travel slower than
the advective velocity).
• Bi-polar water molecules can similarly be retarded
giving rise to osmotic and membrane filtration
effects.
 Electrokinetic Effects
-
Clay Surface -
-
- - Pore
Clay A -
Pore -
- +
- - -
+
Clay -
A’ + -
- + -
- -
- -
+ -
-
Clay Surface
Velocity

- -

- Anion
Distance AA’ + Cation
 Dispersion Concepts

Velocity
• Mechanical dispersion
spreads mass within a
porous medium in two Position in Pore
ways:
– Velocity differences
within pores on a
microscopic scale.
– Path differences due to
the tortuosity of the pore
network.
 Macroscopic Dispersion

• Random variations in velocity and tortuous paths

through flow systems are created on a larger scale
by lithological heterogeneity.
• Heterogeneity is responsible for macroscopic
dispersion in flow systems
 Experimental Continuous Tracer
INFLOW A OUTFLOW B
1 1
C/Co

C/Co
0 0
Time Time
Start Start

A B
 Continuous Tracer Test
• First tracer C/Co > 0.0 arrives faster than
advective velocity.
• Mean tracer arrival time C/Co = 0.5
corresponds to advective velocity.
• Last tracer C/Co = 1.0 travels slower than
advective velocity.
• First tracer C/Co > 0.0 arrives faster than advective
velocity.
• Mean tracer arrival time C/Co = 0.5 corresponds to
advective velocity.
• Last tracer C/Co = 1.0 travels slower than advective
velocity.
t = t1

t = t2
C/Co = 1 C/Co = 0

t = t3
 Experimental Pulse Tracer
INFLOW A OUTFLOW B
1 1
C/Co

C/Co
0 0
Time Time
Start Start

A B
 Pulse Tracer Test
• The “box function” of the source is both delayed and
attenuated by dispersion.
• The pulse peak arrival time corresponds to the
advective velocity.
• The peak concentration C/Co is less than 1.0
• The breadth and height of the peak characterize the
dispersivity of the porous medium.
 Pulse Tracer Transient
t = t1

t = t2
C/Co = 0 C/Co = 0

t = t3
 Pulse Zone of Dispersion
• The zone of dispersion broadens and the peak
concentration C/Co reduces as it moves
through the porous medium.
• Ahead of the zone C/Co = 0
• Behind the zone C/Co =0
Transverse and Longitudinal Dispersion
 Diffusion Law
• Darcy’s law for relates fluid flux to hydraulic gradient:
q = -K dh/dx
• For mass transport, there is a similar law (Fick’s law)
relating solute flux to concentration gradient in a
pure liquid:
J = -Dd. dC/dx
where J is the chemical mass flux [moles. L-2T-1]
C is concentration [moles.L-3]
Dd is the diffusion coefficient [L2T-1]
 Molecular Diffusion
• Molecular diffusion is mixing caused by random
motion of solute molecules as a result of thermal
kinetic energy.
• The diffusion coefficient in a porous medium is less
than that in pure liquids because of collisions with
the pore walls.
J = -Dd.[n dC/dx + τ / V]
where V is a chemical averaging volume [moles-1L3],
n is porosity and
τ is the tortuosity of the porous medium.
 Fick’s Law for Sediments
• This theoretical function, for practical
applications, has been simplified to :
J = -D*d.n.dC/dx
where D*d is a bulk diffusion coefficient accounting for
tortuosity
• This form of the function is known as Fick’s law
for diffusion in sediments often written as:
J = -D’d dC/dx = - u.n.Dd dC/dx
where D’d is an effective diffusion coefficient , Dd is the
self diffusion coefficient of the solute ion, n is porosity
and u is a dimensionless factor < unity.
 Estimating D’d

• The factor u depends on the tortuosity of the

medium and empirical values (Hellferich, 1966) lie
between 0.25 and 0.50
• Bear (1972) suggest values between 0.56 and
0.80 based on a theoretical evaluation of granular
media.
• Whatever the factor used, D’d increases with
increasing porosity and decreases with increasing
tortuosity τ = Le/L
 Dd for Common Ions
Cation Dd (10-10 m2/s) Anion Dd (10-10 m2/s)
H+ 93.1 OH- 52.7
K+ 19.6 Cl- 20.3
Na+ 13.3 HS- 17.3
HCO3- 11.8
Ca2+ 7.93 SO42- 10.7
Fe2+ 7.19 CO32- 9.55
Mg2+ 7.05
Fe3+ 6.07
Typical factors to calculate D’d are 0.10 to 0.20 for granular materials
Notice that diffusion coefficients are smaller the higher the charge on the ion
 Mechanical Dispersion
• Mechanical dispersion is caused by local
variations in the velocity field on scales
ranging from microscopic through
macroscopic to megascopic.
• Variations in hydraulic conductivity due to
lithological heterogeneities are the main
sources of velocity variations.
A. Dispersion: spreading of plumes
*water flowing through a porous
medium takes different routes
*important components:
longitudinal & transverse dispersion

 velocity dependent, so equivalent

only for very slow flow

http://www.theshop.net/xibits/litigation/diagrams9.htm

•D* = 10-5 m2/day. (D* = diffusion constant)

• αL = .1m/day (dispersion constant, longitudinal).
• αr = .001m/day (dispersion constant, transverse).
•( αL)(Vx) + D* = DL ---> longitudinal
•( αT)(Vz) + D* = DT ---> transverse
Factors causing pore-scale longitudinal dispersion

Figure 10.8 Fetter, Applied Hydrogeology 4th Edition

 Dispersion Coefficient
• The processes of molecular diffusion and mechanical
dispersion cannot be separated in flowing ground
water.
• For one dimension:

DL = the longitudinal coefficient of hydrodynamic

dispersion
aL = the dynamic dispersivity
vx = the average linear ground water velocity
D’= the effective molecular diffusion coefficient
B. Advection: horizontal velocity

Advective transport and the influence of dispersion and diffusion on

“breakthrough” of a solute

Figure 10.10 Fetter, Applied Hydrogeology 4th Edition

 Hydrodynamic Dispersion
• For one dimension:

C = solute concentration
Co = initial concentration
t= the time since release of solute
L = the flow path length
Transport and spreading of a solute slug with time due to advection and dispersion. A slug
of solute was injected at x = 0 + α at time t0 with a resulting concentration of C0. The
ground-water flow is to the right.

Figure 2.6. Fetter, Contaminant Hydrogeology 3rd Edition

Dispersion and Scale (Scale effect)

• Mechanical dispersion is also caused by

heterogeneities in the aquifer.
• The greater the distance over dispersivity is
measured, the greater the value that is observed
C. Diffusion: function of concentration & diffusion
coefficient
Spreading of a solute slug with time due to diffusion. A slug of solute was injected
into the aquifer at time t0 with a resulting initial concentration of C0.

Figure 2.1. Fetter, Contaminant

Hydrogeology 3rd Edition
http://www.ldeo.columbia.edu/~martins/plumeflow/ppt/ppt2_1_00/sld010.htm
D. Retardation:
KD = concentration absorbed/ concentration dissolved in water = ml/g
•metals attach onto clays.
•contaminants attach onto organic carbons.
•the higher the KD, the slower things will move in water.
 Vx = V(H2O)/ [1 + KD ( ρ/η)]

Influence of retardation on movement of a solute front in a one-dimensional column

Figure 10.14 Fetter, Applied Hydrogeology 4th Edition

 Retardation
• Freundlich isotherm

C* = mass of solute sorbed per

bulk unit dry mass of soil
C= solute concentration
Kf, j = coefficients

Kd = distribution coefficient
 Retardation
• Langmuir adsorption isotherm

C* = the amount of ion adsorbed pr unit weight of soil

(mg/g)
C= the equilibrium concentration of the ion in contact
with soil (mg/L)
β1= the adsorption constant related to the binding
energy
β2 = the adsorption maximum for the soil
• Retardation factor (R)

ρb = dry bulk mass density

θ= volumetric moisture content of soil
Kd = distribution coefficient for the solute with the soil
Vx = average linear velocity
Vc = velocity of the solute front
 Peclet Number
• D/Dd is a convenient ratio that normalizes
dispersion coefficients by dividing by the
diffusion coefficient.
• v.dm /Dd is called the Peclet Number (NPE) a
dimensionless number that expresses the
advective to diffusive transport ratio.
Empirical Data on Dispersion
 Transport Regimes
• For NPE < 0.02
diffusion dominates
• For 0.02 > NPE < 8
diffusion and mechanical dispersion
• For NPE > 8
mechanical dispersion dominates
Some authors place the boundaries at 0.01 and 4 rather than
0.02 and 8
 Velocity Proportionality
• For values of NPE > 8 the longitudinal (and transverse)
dispersion coefficient (DL) is proportional to the
advective velocity (v).
• This result has been generalized to describe
dispersion both on microscopic and megascopic
scales.
• Tranverse dispersion coefficients (DT) are typically
around 0.1DL for NPE > 100 although values as low as
0.0 1DL have been reported.
 Example Problem
• A landfill is leaking leachate with a chloride
concentration of 725 mg/L, which enter an
aquifer with the following properties :
Hydraulic conductivity : 3.0 x 10 -3 cm/s
dh/dx = 0.0020
Effective porosity =0.23
D’= 1 x 10-9 m2/s (estimated)
Compute the concentration of chloride in 1 year at a
distance of 15 m from the point where the leachate enter
the ground water.
Solution