ASTM RBCA MODELS Derivation of the Surficial Soil Volatilization Factor (VFss) By Polo Velasco poveca@aol.

com Introduction All the pathways in the ASTM RBCA process, with exception of the soil leaching to groundwater, require the evaluation of hydrocarbon volatilization from soil and/or groundwater to the soil surface, or to the bottom of the basement or house floor. The ASTM RBCA process uses several volatilization factors, VF, to account for the volatilization of hydrocarbons from the subsurface. The expressions of these volatilization factors are relatively complex, and unfortunately no derivation details are given in any ASTM document. Consequently, it is difficult to infer the physical meaning of these factors, which leads to the blind use of these factors by environmental professionals. Blind use comes from the lack of a clear understanding of how these factors are derived. The purpose of this document is to derive the surficial soil volatilization factor, VFss, to show, as clearly as possible, the physical meaning of this factor. The reason to select the derivation of this volatilization factor is that mathematically this is perhaps the most complicated one to derive, since it involves the solution of a partial differential equation, the diffusion equation. The final objective of this exercise is to help users of the ASTM process understand the assumptions followed to develop this factor. An understanding of the assumptions involved in the determination of this volatilization factor will help the user gain a better appreciation of the physical meaning of the Surficial Soil Action Level (RBSLs). Diffusion Equation The major transport process during volatilization is vapor diffusion. The ASTM process uses the diffusion equation to derive the volatilization factor for the surficial soil volatilization. The solution to the diffusion equation used to derive the ASTMs surficial soil volatilization factor, VFSS, is given below.

In a one-dimensional, homogeneous porous medium, the mass conservation equation, assuming that transport occurs due to vapor and liquid diffusion, may be written as: r e t a w2 x C 2 r e t a w D + r i a 2 C x 2 r i a D = T t C H= C air Cwater C Cwater = air H H is the dimensionless Henrys law constant. Replacing the value of Cwater in equation (1) we get: Lets make the portion in parenthesis equal to D: Then equation (3) becomes:

The portion of the hydrocarbon dissolved in the soil pore water is assumed to be in equilibrium with the portion present in the soil air in accordance with Henrys law:

r i a 2 C x 2 r e t a H w D + r i a 2 C x 2 r i a D = T t C
r i a 2 C x 2

= T t C

r e t a H w D + r i a D

r e t a H w D + r i a D
2

= D

r i a 2 C x 2 D = Tt C

The diffusion coefficient D accounts for the diffusion effect in free air, Dair, and in free water, Dwater. However, diffusion in soils is affected by soil tortuosity. Tortuosity is caused by the reduction in the flow area, due to the presence of pore water, and by the increase in path length of diffusing gas molecules in the soil. Several models have been proposed to account for the effect of tortuosity. The ASTM methodology uses the following tortuosity factors, , for air and water, derived by Millington and Quirk:
r 0 i 1 3a
0 a 1 3w

l i ro i a s

r e t l i a o ws

r e t 2T

2T

Where:
air = t n e t n o c r i a c i r t e m u l o v
10

water = volumetric water content T = total porosity = air + water

Using the values derived by Millington and Quirk, then the true diffusion coefficients in air and water in the soil are:

D air

air T
2

10 3

D water and H

3 air

, respectively

If we introduce these parameters in equation (4), we get the effective soil diffusion coefficient, Ds , presented in the ASTM document:
eff

eff D s = D air

air
2 T

10 3

3 D water air

10

Replacing D for Ds

eff

in equation (5) gives:

In order to solve this partial differential equation it is necessary to express the total soil concentration, CT, (Total Mass of Solute / Total Soil Volume) in terms of the soil air concentration Cair. The total soil concentration is given by the following equation:

C T = C air

b K oc foc

Lets make the term in parenthesis in (7) equal to P, then we get:

Introducing in equation (6) the value of C T given in (8) we get:

The solution of this partial differential equation depends on the initial and boundary conditions used. The ASTM uses the initial and boundary conditions presented below to solve this equation. Surficial Soil to Ambient Air Exposure Pathway In the ASTM methodology it is assumed that the soil is a semi-infinite solid bounded by the planes x = 0, and x = , with an initial constant soil gas concentration equal to Co. Thus for t= 0 then C (x, 0) = Co, and for t>0 the concentration at the surface is kept a zero. C (0, t) = 0

r i a 2 C x 2 f f e s D = T t C
H

+ water + air H

(7)

P r i a C = T C
f f e s P D

r i a 2 C x 2

= r i a t C

The solution of equation (9) using these initial and boundary conditions is:

X
1

Cx

To obtain the contaminant flux from the source we need to know the value of Therefore, we need to derive C with respect to x:

f r e o C = C = Cx
Then for x = 0, we get:

t f f e sP D

t f f e sP D 4 2 x -

12 t f o f C es P D

12 t f o f C es P D

The rate of loss of diffusing contaminant at x = 0 is given by Ficks first law

0 = x Cx f f e s D = F

Cx

x=0

=
5

12 t f o f C es P D

f f e s D = F

The average flux over time F is obtained by integrating F over time from: t = 0 to t = and dividing by :

12

12 t

12 f o f C es P D f o f C e sP D

2 12 f o f C es P D

The average flux of the contaminant at the surface is then given by:
12

The reason to use an average flux is that one can use then a constant flux over the time of exposure to obtain an average constant concentration. The ASTM uses a box mixing model to predict the ambient air concentration Cair down gradient from the mixing zone.

Cair outside = 0 Wind direction V

The box in which the mixing occurs has a length W, a height , and a unit width. The mass of contaminant entering the box is equal to x 1 and the mass of

contaminant leaving the box is equal to

f f e s D = F

f f e s D =

12 f f e s P D o C 2 = 12

f f e s D 2 = F

f f e s P D o C 2 = F

W C air Uair Cair V = Wind velocity

F
F 1 x r i a C
6

W x
.

The mass balance in the box is given by:

12

r i a C

Then the contaminated ambient air concentration Cair is:

It is more practical to define the soil gas concentration at the source CO in terms of CT, or total soil contaminant concentration at the source.

W x F

Cair = 2 Co

V = 1 x

1 x

f f e s P D

r i a C

o C 2

eff Ds P

W V

(10)

H r i a + r e t a w b + cH o f c o K b o C = T C

b P

o C = T C

b P T C = o C

Replacing the value of as a function of

o C

in equation (10) we obtain the ambient air concentration 1

CT is then obtained from this equation as:

The denominator in the equation given above is the volatilization factor VFSS:
Deff s VFSS = 2 b P 2 W V

If we introduce in this equation the value of P given in equation (7), we get the ASTM Surficial Volatilization Factor: 1

VFSS = 2 * b *

T C

:
C T b Deff s C air = 2 P P 2 W V 2 W V

Deff s C air = 2 C T b P

r i a C

2 Deff *H W s V* * K * f + * * + H * oc oc water air b

= T C

W V 12

f f e s D P b 2
8