Solute Transport

There are three basic mechanisms that affect solute transport in soils: Mass Flow Molecular Diffusion Hydrodynamic Dispersion (Dispersivity)

The solute flux (Js) is essentially controlled by the various mechanisms of liquid flux (Jl) and gaseous flux (Jg). Js = Jl + Jg

The solute liquid flux consists of that due to liquid convection (Jlc), dispersion (Jlh), and diffusion (Jld), such that:
Js = Jlc + Jlh + Jld + Jg where for non-volatile chemicals Jg 0

Jlc = JwCl

where Jw = -K()H, and Cl = concentration of the solute in solution Dlh= dispersion coefficient Dld= diffusion coefficient De = combined dispersivity coefficient Dg = gaseous diffusion coefficient

Jlh = -DlhC/x Jld = -DldC/x Jdh = -DeC/x Jg = -DgC/x

Time Dependent Solute Flux Just as for transient state water flow, time dependent solute flux is derived from the conservation of mass theory.
z

Js
y x

Js

CT/t = - Js/x,y,x r
where r = internal reactions

Horizontal Solute Flux

CT/t = -Js/x r
where Js = JwCl - DeC/x - Dg C/x and CT/t = -/x (JwCl - DeC/x -DgC/x) - r

NOTE: Solute flux due to dispersivity and gaseous diffusion are normally small in comparison to the mass transport due to liquid water flow.

Inert, Non-Volatile, Non-Adsorbing Solute Inert = Not chemically reactive; r = 0

Non-Volatile = Remains in solution; Jg = 0

If the solute concentration is low and water flow is due to gravity alone:

Js = Jw = -K()H
Average velocity (v) = Jw/

Average Residence Time (time to breakthrough)

tb = L/v = L/Jw
where H = 1 and Jw = K() such that tb = L/K() and the distance L L = tbK()/

Inert, Non-Volatile, Adsorbing Solute In this instance, solute transport is delayed due to the adsorption process: v = v/(1+k) where k is the adsorption coefficient (selectivity constant). Hence, tb = ((1+k)L)/K() and

L = tbK()/((1+k)())

How do we determine the value of k? If the solute is cationic and the adsorption mechanism is non-specific we can apply a cation exchange equation to determine the equilibrium constant k. If the adsorption mechanism is specific we can develop an adsorption isotherm to determine k (simplest form is linear).

Whereas the effect of adsorption is to delay the time to breakthrough, dispersivity imparts a spreading or tailing effect as a result of variable flow velocities and liquid diffusion. Non-Adsorbing Solute

CT/t = -JwCl/x + /x [DeCl/x]

where v = Jw/ and D = De/ and since there is no adsorption 0 CT/t = /t(bCa+Cl) (Cl)/t = -vCl/x + D2Cl/x2

Adsorbing Solute /t(bCa+Cl) = -vCl/x +D2Cl/x2 If we assume a linear adsorption isotherm: Ca/t = k Clt

such that
(1+kb/)Cl/t = -vCl/x +D2Cl/x2 Defining a new varialble r = (1+kb/) rCl/t = -vCl/x +D2Cl/x2

Methods of Study Breakthrough Curves

A steady water flow regime is established in a soil column, and at some time (t0), solute is suddenly added to the input. t0
By analyzing the effluent at various times (t>t0, the shape of the curve showing the appearance of solute at the outflow is characterized.

Pore Volume A pore volume is defined as the amount of water which must be added in order to move salt a given distance L (length of the soil column). 1PV = L* Piston Flow Piston flow refers to the approximate model which neglects all but the mass water flow component of the solute flux. In this model, when a slug of water is added, all the solute suddenly appears at the distance L.

Breakthrough Time (tb) The breakthrough time is defined as the time after which salt is added to the inlet and it first appears at the outlet. According to the piston flow model, tb = L/v = L/Jw
1.0 Piston Flow Model The spreading effect is due to liquid diffusion and dispersion (dispersivity). Actual Breakthrough

c/c0

tb

This oversimplification applies primarily to inert non-adsorbing solutes. Follow-up solute free leaching of the soil column would typically result in a more or less mirror image of solute discharge.
Leaching Begins 1.0

c/c0
Average time to breakthrough

tb (or PV of solution)

The effect of adsorption on breakthough is to delay the time of solute appearance at the column outlet.

c/c0

NonAdsorbing Solute
time lag shift

Adsorbing Solute

tb

tb

In the case of a linear adsorption isotherm:

bCa = kCl
(amount adsorbed) = k (amount in solution) where k may be taken as the average slope of the breakthrough curve. Hence, the effective velocity (v) of the solute is reduced to:

v = v/(1+k)
and tb = L/v = (1+k)L/K()

Depending on the reversibility of the adsorption process, column leaching may take on a different character.
Leaching Begins Somewhat Irreversible Strongly Irreversible

c/c0

tb

Example Calculation Calculate the breakthrough time for a front of solute moving through a vertical soil column, 100 cm in length of saturated conductivity Ks = 5 cm/hr, s = 0.50, and inflow pressure head of 10 cm.
b = 10 cm A = 100 cm2 K = 5 cm/h L = 100 cm

= 0.50

Js

In the absence of rapid and turbulent water flow, for an inert non-adsorbing solute Js = Jw Hence, Jw = -KsH

where H1 = 0 and H2 = 10 cm + 100 cm.

Jw = -5 cm/h (110 cm/100 cm) = -5.5 cm/h v = Jw/ = (5.5 cm/hr)/0.50 = 11 cm/h tb = L/v = 100 cm/11 cm/h = 9.09 h

Example Calculation Next, consider that there is a 1 mm diameter wormhole extending through the column and through which water flows according to Poiseuilles Law.
b = 10 cm A = 100 cm2 K = 5 cm/h L = 100 cm

1 mm diameter wormhole

= 0.50

Js

The liquid volume flow rate through the wormhole is given by: Q = ((R4/8)lg)(b+L/L) = 0.265 cm3/s and the average velocity is

v =Q/R2 = 33.7 cm/s

Hence, tb = 2.97 s Structural voids clearly have a dominant effect on water and solute flow if fully conducting.

Effects of Cation Exchange on Breakthrough Characteristics

Cation exchange is, in effect, an adsorption process. As such, it can be qualitatively described by observing what happens when a multi-electrolyte solution is moving through a porous medium. Consider the following scenario:
Na2SO4 Na Na Na Na Na Na Na SO4 SO4 SO4 SO4 SO4 SO4 CaCl2 Ca Na Na Ca Na Na Na SO4 Cl2 Cl2 SO4 SO4 SO4

Na2SO4

CaCl2

2NaX + Ca CaX + 2Na

1.0
SO4 Na Cl

C/C0

Ca tb = L/v

tb = (1+k)L/(K()

For more complicated systems we must also consider the effects of diffusion and dispersion which would tend to flatten the breakthrough characteristics and to contribute to a tailing-off effect as well.

Similar effects are observed in aggregated soil where water tends to flow through restricted channels by-passing part of the porous medium. Solutes then move into and out of these stagnant regions only by diffusion, thus creating a tailing effect.

1.0
Compacted

C/C0
Aggregated

Profile Distribution Measurements

This technique generally uses a sectional soil column where the solute is initially applied to the top of an initially dry soil column at a rate <Ks. For a non-adsorbing solute, C/C0 1.0 in each section down to the wetting front.
C0 C C C C C C 1.0 Wetting Front

C/C0
Wetting Front Z

For an adsorbing solute the distribution profile is quite different. Here the amount on the adsorbed phase is initially high at the point of inflow, then decreases with depth at a rate dependent on the distribution coefficient k.
The greater the distribution coefficient the more strongly sorbed, the higher the amount on the sorbed phase in the initial sections of the soil column and the more rapid the decline in amount adsorbed with depth.

Ca (g/g)
k1

k2

k1>k2>k3 k3

Upon leaching, the long-term effect is to more evenly distribute the solute throughout the entire soil column. The rate at which one can attain this effect also is dependent upon the distribution coefficient.

Characteristically, a weakly sorbed solute will move downward in a wave-like fashion rapidly attaining a more-or-less uniform distribution with depth. For more strongly sorbed solutes, the wave will move much more slowly with a prominent peak of maximum concentration at depth over a much longer time period.

k2 >>> k1 Ca (g/g)
C0 C1 C0 C1 C2 C3 k1 k2

C2