CWR 6537 Subsurface Contaminant Hydrology

Lecture 12

ADVECTIVE-DISPERSIVE TRANSPORT OF NON-CONSERVATIVE SOLUTES:

I. Simple Reactions

So far we have examined the advective-dispersive transport of conservative nonadsorbed

and adsorbed solutes. We will now discuss the transport of nonconservative solutes.

A solute is said to be nonconservative if the solute is "created" and/or "lost" during flow
through soils. For example, microbial degradation of pesticides, denitrification of nitrate,
nitrification of ammonium, plant uptake of nutrients would all lead to a "loss" of solute. Such
processes are termed "sinks". Solute may be created such as by solubilization of gypsum or
crystalline and solid forms of salts and fertilizers, mineralization of org-N to yield nitrate, etc.
These processes are examples of "sources" which increase the solute concentration during flow.

Total solute present in a unit volume element of soil is the sum of solution-, adsorbed-
phases and the net losses (or gains) due to sinks/sources.

TOTAL SOLUTE = SOLUTION PHASE + ADSORBED PHASE ± SINKS/SOURCES

mass/cm3 mass/cm3 mass/cm3

∂M ∂ ∂
= ( θC ) + ( ρS ) ± φ (1A)
∂t ∂t ∂t

As before, the solute flux is due to convection and hydrodynamic dispersion. Thus,

 ∂C 
J T =  - θD + qC  (1B)
 ∂x 

∂M ∂J
=- T (1C)
∂t ∂x

From continuity equation,

∂ ∂ ∂  ∂C  ∂
∴ ( θC ) + ( ρS ) = θD  - (qC ) ± ϕ (2)
∂t ∂t ∂x  ∂x  ∂x

The sink/source term, ϕ, has units of ML-3T-1, the same as other terms in the transport equation.

For steady-water flow conditions, ∂θ/∂t = 0,

∂C ∂S 2
∂ C ∂C
θ +ρ = θD -q ±ϕ (3A)
∂t ∂t ∂x 2
∂x

or,

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 CWR 6537 Subsurface Contaminant Hydrology
Lecture 12

∂C p ∂S 2
∂ C ∂C ϕ
+ =D -v ± (3B)
∂t θ ∂t ∂x 2
∂x θ

Eq.(2) is pertinent to transient water flow, while Eq.(3) is applicable for steady water flow. In
order to solve Eqs. (2) or (3), we need to mathematically (i.e., conceptually) specify (∂S/∂t) and
ϕ. Thus, sorption and sink/source processes need to be quantitatively described.

Let us assume linear, reversible, and instantaneous sorption. That is,

∂S ∂C
S = K D C and = KD (4)
∂t ∂t

Consider the sink/source term, ϕ, to be described by a first-order process. That is,

φ=-kθ C (5)

where, ϕ is rate of loss (e.g., degradation), k is first-order rate coefficient (T-1), θ is volumetric
water content (L3L-3), and C is solution concentration (ML-3).

Substituting Eq.(4) and (5) in (3) yields,

∂C ρ K D ∂C 2
∂ C ∂C
+ =D -v -kC (6)
∂t θ ∂t ∂x 2
∂x

or,

ρ K D ∂C 2
∂ C ∂C
(1 + ) =D -v -kC (7)
θ ∂t ∂x 2
∂x

Letting R = (1+ρKD/θ), D* = D/R, v* = v/R, and k* ≠k/R. Eq.[7] becomes,

∂C 2
∂ C ∂C
= D* - v* - k* C (8)
∂t ∂x 2
∂x

For steady-state conditions (i.e., ∂C/∂t = 0),

2
∂ C ∂C
D* - v* - k* C = 0 (9)
∂x 2
∂x

or,

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 CWR 6537 Subsurface Contaminant Hydrology
Lecture 12
2
∂ C ∂C
D -v - k C=0 (10)
∂x 2
∂x

For steady-state conditions, the sorption (retardation term, R) effect vanishes.

CASE I: CONTINUOUS APPLICATION:

C (x,t) = 0 ; 0 ≤ x < ∞ ; t < 0 (11a)

C (x,t) = Co ; x = 0 , t ≥ 0 (11b)

The solution to Eq.[8] subject to [11] is (Cho, 1971):

C 1
= [exp ( ξ 1 ) ⋅ erfc ( ξ 2 ) + exp ( β 1 ) ⋅ erfc ( ξ 2 )] (12)
Co 2

where,

 x
ξ 1=  ( 2 1/2 
v* - ( v* + 4 D* k* )  ) (13)
 2 D* 

 x - t ( v*2 + 4 D* k* )1/2 
ξ2=   (14)
 (4 D* t )1/2 

β 1= 
 x
( 2 1/2 
v* + ( v* + 4 D* k* )  ) (15)
 2 D* 

 x + t ( v*2 + 4 D* k* )1/2 
β2=   (16)
 (4 d * t )1/2 

For large distances (x) and times (t), the second term in Eq.[12] may be neglected. Thus,

C 1
= [exp ( ξ 1 ) ⋅ erfc ( ξ 2 )] (17)
Co 2

For steady-state conditions (∂C/∂t = 0), the solution to Eq.[10] is:

ξ1
C ( x) = C o e (18)

or,

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 CWR 6537 Subsurface Contaminant Hydrology
Lecture 12

x
(υ −(υ 2 + 4 Dk )1 / 2 )
C(x) = C o ⋅ e 2 D (19)

Eqs. (18) – (19) are time-independent. When, 4Dk « v2 , Eq.(19) reduces to:

 kx 
C(x) = C o ⋅ exp  -  (20)
 v 

Some calculated C(x) curves are shown in Figures 1 and 2.

CASE II: PULSE APPLICATION:

∂C 2
∂ C ∂C
= D* - v* - k* C (21)
∂t ∂x 2
∂x

C(x,t) = 0 ; x ≥ 0 ; t ≤ 0 (22a)

C(x,t) = Co ; x = 0 ; 0 < t ≤ T (22b)

C(x,t) = 0 ; x = 0 ; t > T (22c)

C(x,t) = 0 ; x → ∞ ; t ≥ 0 (22d)

The solution to Eq.(21) subject to (22) is (Misra et al., 1974):

C ( x, t )
= P ( x, t ) ; 0 < t ≤ T (23)
C0

and,

C ( x, t )
= [P( x, t ) − P( x, t − T )] ; t > T (24)
C0

where,

1
P(x,t) = [exp ( ξ 1 ) ⋅ erfc ( ξ 2 ) + exp ( β 1 ) ⋅ erfc ( β 2 )]
2

ξ1 , ξ2 , β1 , and β2 are as defined by Eqs.[13] - [16].

To obtain P(x, t-T), in the above equation replace t by (t-T).

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 CWR 6537 Subsurface Contaminant Hydrology
Lecture 12

II. Complex Reactions

The concepts presented earlier for simple reactions will now be extended for complex and/or
coupled reactions. As examples, three cases will be examined.

CASE I: SINKS AND SOURCES

Consider first-order loss from both solution- and adsorbed phases as well as zero-order
production into solution-phase. For steady-water flow conditions:

∂C ρ ∂S 2
∂ C ∂C βρ
+ =D -v -α C - S+r (25)
∂t θ ∂t ∂x 2
∂x θ

Assuming linear, instantaneous-reversible sorption,

∂S ∂C
S = KD C ; = KD (26)
∂t ∂T

∂C 2
∂ C ∂C  βρ K D 
R =D -v - α + C+r (27)
∂t ∂x 2
∂x  θ 

 βρ K D 
Letting, µ = α +  , where µ is the combined degradation (loss) rate coefficient for
 θ 
solution and adsorbed phases

∂C 2
∂ C ∂C
R =D -v - µ C+r (28)
∂t ∂x 2
∂x

For a semi-infinite medium (0 ≤ x < ∞) and flux boundary conditions:

C(x,t) = Ci ; 0 ≤ x < ∞ , t = 0 (29)

∂C
−D + vC = vC 0 ; 0 < t ≤ T
∂x (30,31)
=0 ; t >T

∂C
= 0; x → ∞, t > 0 (32)
∂x

The solution to Eq.(28) subject to (29) – (31) is:

(Co - r/µ) A(x,t) + B(x,t) ; 0 < t ≤ T (33a)

C(x,t) =

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 CWR 6537 Subsurface Contaminant Hydrology
Lecture 12

(Co - r/µ) A(x,t) + B(x,t) - Co A(x,t-T), t >T (33b)

where,

 v   (v - u)x   Rx - ut 
A(x,t) =   exp  erfc  1/2 
 v+u   2D   (4DRt ) 
 v   (v + u)x   Rx + ut 
+  exp  erfc  1/2 
(34)
 v-u   2D   (4DRt ) 
 v2   vx µt   Rx + vt 
+   exp  -  erfc  1/2 
 2 µD  D R   (4DRt ) 

and,

r   µt   1  Rx - vt 
B(x,t) =  - C i  exp -   erfc  1/2 
µ   R  2  (4DRt ) 
1/2
 v2 t   (Rx - vt )2 
+   exp -  (35)
 πRD   4DRt 
1 vx v2 t   vx   Rx + vt  
-  1 + +  exp   erfc  1/2  
2 D DR  D  (4DRt )  
r  r  µt 
+ +  C i -  exp  - 
µ  µ  R

and,

1/2
 4 µD 
u = v 1 + 2  (36)
 v 

To obtain A(x, t-T) , in Eq.(34) replace everywhere (t-T) for t.

The steady-state solution for this case (i.e., ∂c/∂t ≡ 0) is,

r  r   2v   (v - u)x 
C(x) = +  C o -    exp  (37)
µ  µ   v+u   2D 

For the case of r ≡ 0, (i.e., no source term), in Eqs.(29), (33 – 37), simply set r ≡ 0 to obtain the
analytic solution. Note also that the steady-state solution is independent of R (adsorption-
desorption) term.

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 CWR 6537 Subsurface Contaminant Hydrology
Lecture 12

CASE II: CATENARY REACTIONS:

We will now examine coupled transformations and transport of two or more solutes.

∂ C1 ∂ C1 ∂ C1
2
(1 + R1 ) = D1 -v - k 1 C1 (38)
∂t ∂ x2 ∂x

ρKD/θ
NOTE: Unlike in earlier notes, R1 = (ρ θ).

∂ C2 2
∂ C2 ∂ C2
= D2 -v + k1 C1 - k 2 C 2 (39)
∂t ∂x 2
∂x

C1=Co , C2=Co 2 ; x=0 , 0<t<t1

C1 = C2 = 0 ; x=0 , t>t1
C 1 = C2 = 0 ; x ≥ 0 , t = 0 (40)
C 1 = C2 = 0 ; x → ∞ , t ≥ 0

The analytical solutions to Eq.(39) and (40) subject to (41) are given by Misra et al. (1974). Cho
(1971) presented the solution for continuous input.

Analytical solutions for the steady-state (∂C/∂t ≡ 0) condition may be derived for a continuous
solute input. See Starr et al. (1974).

2
d C1 dC 1
D 2
-v - k1C = 0 (41)
dx dx

2
d C2 dC 2
D 2
-v + k 1 C1 - k 2 C 2 = 0 (42)
dx dx

C = C10 , C2 = 0 ; x = 0 , t ≥ 0 (43)
C1 = C2 = 0 ; x>0 , t=0

0  x
C 1 (x) = C 1 exp  ( 1/2 
v - ( v2 + 4 Dk 1 )  ) (44)
 2D 

when, Dk1 <<< v2,

C1(x) = C10 exp (-k1 x/v) (45)

 k 1 C 01  
C 2 (x) = 
 x
 exp  (v - ( v 2 + 4 Dk 2 )1/2 ) (46)
 k1 - k 2    2D 

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 CWR 6537 Subsurface Contaminant Hydrology
Lecture 12

 x
- exp  ( )
1/2 
v - ( v 2 - 4 Dk 1 ) 
 4D 

Again for Dk1 <<< v2 ,

 k 1 C 01    x  x 
C2 (x) =   exp  - k 2  - exp  - k 1  (47)
 k1 - k 3    v   v 

 2
∂ 
Note from Eq.(41) that a plot of  D ∂ C21 - v C 1  versus C1 will yield a straight line with slope
 ∂x ∂x 
= k1

See: * Selim & Mansell (1976), WRR 12:528, for an analytical solution for finite
column with flux boundary condition

* van Genuchten and Cleary (1979), for analytical solution for flux boundary
condition and semi-infinite columns IN: SOIL CHEMISTRY B. Physico-chemical
Models Ed. G.H. Bolt. Elsevier Sci. Publ. Co.

CASE III: CYCLIC TRANSFORMATIONS AND TRANSPORT:

∂ C1 ∂ C1 ∂ C1
2
(1 + R1 ) = D1 -v - ( k 1 + k 3 ) C1 + k 4 C 3 (48)
∂t ∂ x2 ∂x

∂ C2 2
∂ C2 ∂ C2
= D2 -v + k1 C1 - k 2 C 2 (49)
∂t ∂X 2
∂x

∂ C3
= k 3 C1 + k 2 C 2 - k 4 C 3 (50)
∂t

Let us assume ki are not constants as before, but let them decay exponentially with depth.

i ax exp (-βix)
ki(x) = km (51)

Note that

1L k imax
ki = ∫k
L0 i
(x)dx =
βi L
[
1 - exp (- β i L) ] (52)

SEE: Rao et al. (1975) SCSSF Proc. 35:161-164

Mehran and Tanji (1974) JEQ 3:391-395