AppI. Math. Lett. Vol. 10, No. 1, pp.

31-34, 1997
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Pergamon

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PII: S0893-9659(96)00106-1

M o d e l l i n g t h e V o l a t i l i z a t i o n of Organic
Soil C o n t a m i n a n t s : E x t e n s i o n of t h e Jury,
S p e n c e r and F a r m e r B e h a v i o u r A s s e s s m e n t
M o d e l and S o l u t i o n
R. S. ANDERSSEN AND F. R. DE HOOG
CSIRO Division of Mathematics and Statistics
GPO Box 1965, Canberra, ACT 2601, Australia

B. R. MARKEY
Contaminated Sites Section
Environment Protection Authority NSW
P.O. Box 1153, Chatswood, NSW 2057, Australia

(Received and accepted March 1996)

Communicated by G. C. Wake
A b s t r a c t - - I n the analysis of the volatilization of organic soil contamination, the Behaviour Assessment Model (BAM) of Jury, Spencer, and Farmer [1] has proved to be a valuable exploratory
tool, because it has an analytic solution which is easily and quickly evaluated. However, because
the surface boundary condition in the BAM is homogeneous, its applicability is limited to situations
where the above ground concentration of the volatilant is zero above a boundary layer. The important situations of the accumulation of the volatilant below buildings, in vegetation or below material
stored on the ground are thereby excluded from consideration. This paper derives an analytic solution for the nonhomogeneous surface boundary condition extension of the BAM which allows its
exploratory potential to be extended to the more realistic scenarios mentioned above. This analytic
solution contains the BAM solution as a special case.

Keywords--Convection-diffusion, Explicit analytic solution, Nonhomogeneous surface boundary

conditions, Soil contamination, Volatilization.

INTRODUCTION
I n assessing the p o t e n t i a l health risk associated with emissions of organic soil c o n t a m i n a n t s , the
m a j o r initial step is the modelling a n d solution of the volatilization processes which generate the
emissions.
A n u m b e r of models have been proposed a n d utilized by various a u t h o r s for s i m u l a t i n g the
v o l a t i l i z a t i o n of organic soil c o n t a m i n a n t s (see [2-5]). T h e y include the o n e - d i m e n s i o n a l semii n f i n i t e - d e p t h model of J u r y et al. [1,5] for the p r o t o t y p e s i t u a t i o n where the d e g r a d a t i o n rate
c o n s t a n t # of the c o n t a m i n a n t , its effective diffusion coefficient DE, a n d its effective solute conv e c t i o n velocity V~ are a s s u m e d to be constant. It is of p a r t i c u l a r interest, since the a u t h o r s
derive a n explicit a n a l y t i c solution which has found application in c o n t a m i n a t e d sites exposure
assessment (cf. [6]).
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31

32

R . S . ANDERSSEN et al.

The purpose of this paper is to extend the Jury et al. [1,5] model to a more representative onedimensional situation, and to construct, for this extension, an analytic solution which contains
the Jury et al. [1,7] solution as a special case. The extension presented here is more comprehensive than that considered by Lin and Hildemann [8], in that it allows for the surface-boundary
condition to be nonhomogeneous.

THE

BEHAVIOUR

ASSESSMENT

MODEL

[1]

In a detailed and comprehensive study of the volatilization of a soil contaminant, Jury et al. [1]
proposed the following parabolic partial differential equation, which underpins their Behaviour
Assessment Model:
OC
_ O2C
OC
a--T + ~ c =
- v~-~z,

D~-~z2

C=C(z,t),

O<z<c~,

t_>O,

(1)

with initial condition

C(z,O)={Co, O<z<L,
O,

Co

constant,

L < z < oo,

(2)

with surface-boundary condition

--DE -~z z=O

+ VEC(O, t) = -HEC(O, t),

t _> O,

(3)

and with inner-boundary condition

c(~,t)

= o,

t >_ o,

(4)

where
the total concentration in the soil of the volatilizating contaminant;

C
DE

the effective diffusion coefficient of the contaminant;

HE

h/RG, the gas steady-state behaviour of the contaminant;

DA/d;
the depth of the surface-boundary layer of air;

d=
D A
G =

the diffusion coefficient for the vapour through air;

RG

the partition coefficient for the gaseous concentration relative to the total;

vE= the effective solute velocity of the contaminant; and

the degradation rate constant of the contaminant.
Volatilization at the surface in the Jury et al. [1] model, is assumed to take place via diffusion
through a stagnant boundary layer into an overlying atmosphere where the concentration is
taken to be zero. The above surface-boundary condition, therefore, follows from Fick's law
(cf. [9, Section 1.2]), after approximating the spatial derivative of the concentration C across
the boundary layer (see [1]). The resulting surface-boundary condition (3) represents a balance
between the surface vapour flux (the left-hand side of (3)) and the effect of the boundary layer
(the right-hand side of (3)). However, the homogeneity of this boundary condition excludes from
consideration the important practical situations, where the volatilant on leaving the ground,
accumulates below buildings, in vegetation or below material stored on the ground.
As the solution to their model, Jury et al. [1,7] gave, without proof, the following explicit
expression:
1
C(z, t; L) = ~ Co exp ( - # t ) {C1 (z, t) + C2(z, t) + C3(z , g)},
(5)

Modelling the Volatilization

33

where
Cl(Z,t) = erfc

2 Dv/_D__
~

erfc k ~

C2<z't): (I+-~E)expk, DE ]
Cj(z,t)

2+ ~E

-2~

erfc(2--D~Et]]'

DE

exp

[erfc(Z+(2HE+VE)t)
2,/DEt

(HEL~
-- exp \ DE / erfc

( +L+(2HE+VE)t)]
z
2v/DE t
.

However, no formal derivation of this result was given by these authors.

EXTENSION

OF

THE

JURY

MODEL

[1,5]

Though the Jury et al. [1,5] model is a quite comprehensive representation of the processes
involved, it has some minor, but nontrivial, shortcomings; namely,
(i) the initial distribution of the contaminant C(z, 0) in the soil is assumed to be constant
down to a finite depth L and zero below;
(ii) the surface-boundary condition (3) is homogeneous.
These shortcoming are removed on replacing the above initial and surface-boundary conditions
by
C(z, O) = f(z),
0 < z < oo,
(6)
~tnd

--DE l o~ Zc i

z=O

+ vzc(o,

t) = -HzC(O, t) + ~c+(t),

t >_O,

(7)

respectively, where C+(t) denotes the gas concentration at the upper surface of the stagnant
boundary layer through which the vapour diffuses after leaving the soil. In the above derivation
of equation (7), the Jury et al. [1] framework for the surface-boundary condition has been followed.
In order to solve the above model, the first step is to apply the transformation

(--,/-D--EE'

c(,t)=exp((p+c~2)t)exp(ct()C

x/-D~E(,t ,

c~-

2v/-D~
z,

(8)

which yields
~C

at

C~2C

---

o( 2

c=c(,t),

0<(<~,

t>0,

(9)

0 < (" < oo,

(10)

with initial condition

C(~,0) = exp (a) f (X/~E~) ,
with surface-boundary condition

[Oqc] +hc(O,t)=exp((#+c~2)t)

hC+(t)

N~=0

v~DT~ '

h-

lie

2HE

2x/-~

'

t_>O,

(ii)

and with inner-boundary condition

c (oo, t) = 0,

t > 0.

(12)

This canonical parabolic partial differential equation has an explicit solution given by equation (7) of Section 14.2 in [10]. Transforming this solution back to the original framework defined
by (1),(6),(7), and (4), one obtains

(oz)

C(z,t)=exp ~

exp

(- (~ + ~2) t) {Fl(z,t)+F2(z,t)-Fa(z,t)+F4(z,t)-Fs(z,t)},

(13)

34

R.S. ANDERSSENet al.

where
2 ~--D--~Et

F2(z,t) -- 2 ~x/r~-D~t fo
v/-D--~E

exp

~-/~

exp

4/~7

"]J exp \ x / - ~ , ] f(z')dz',

V~E

/ erfc [2 DVFD~E
t +h

exp th: +

)j

exp ~ V ~ E ]

I(z')dz',

exp \x/-D--~E]

F4(z, t) = h ~ot exp (--z2/4DE

(t -- T)) exp ((# + a2) ~) ~hC+(T) d~-,
~--~
F5(z,t) = h2

exp

exp

h2 ( t - - T) +

+.2)

erfc

--~--E

2v/DE(t_

T) + h

dr.

The analytic solution (5) can now be derived as a special case of (13) (cf. [11]).
REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.

W.A. Jury, W.F. Spencer and W.J. Farmer, J. Environ. Qual. 12, 558-564, (1983).
R. Mayer, J. Letey and W.J. Farmer, Proc. Soil Sci. Soc. of Amer. 38, 563-568, (1974).
W.A. Jury, W.F. Spencer and W.J. Farmer, J. Environ. Qual. 13, 573-579, (1984).
W.A. Jury, D.D. Focht and W.J. Farmer, J. Environ. Qual. 16, 422-428, (1987).
W.A. Jury, D. Russo, G. Streile and H. E1 Abd, Water Resources Research 26, 13-20, (1990).
P.F. Sanders and A.H. Stern, Environ. Toxic. and Chem. 13, 1367-1373, (1994).
W.A. Jury, W.F. Spencer and W.J. Farmer, J. Environ. Qual. 16, 448, (1987).
J.-S. Lin and L.M. Hildemann, J. Hazardous Materials 40, 271-295, (1995).
J. Crank, The Mathematics of Diffusion, Oxford Science Publications, Oxford, (1990).
H.S. Carslaw and J.C. Jaeger, Conduction of Heat in Solids, Clarendon Press, Oxford, (1986).
R.S. Anderssen, Modelling the below-ground volatilization and diffusion of contaminants: Validation and
extension of the Jury et al. (1983, 1987) Model, CSIRO Division of Mathematics and Statistics Report
DMS-E-95/35, Canberra, (1995).