Chapter 7 - Gas Flow: Important Soil Gases

SSC 107, Fall 2002 – Chapter 7 Page 7-1
Chapter 7 - Gas Flow

• Mechanisms of flow
• Fick's Law
• Methods for measuring D
• Diffusion equations
• Diffusion to plant roots
• Consumption or production of gases
• Aeration
• Other diffusion processes
• Water vapor movement
______________________________________________________________________
Important Soil Gases
O2 CO2 H2S NH3 N2 N2O NO CxHy

SO2
O2
CO2
An example of diffusion processes related to contaminants in the vadose zone

Mechanisms for transfer of gases
1. Mass flow in vapor phase
a. Barometric pressure changes

b. Wind
c. Irrigation or rain
d. Production from other chemicals
2. Mass flow in dissolved (liquid) phase
a. Movement with water
3. Diffusion in liquid phase
a. 103 - 104 smaller than diffusion in vapor phase

b. Important in transport of O2 to roots and anoxic denitrification sites
4. Diffusion in vapor phase
a. Probably main mechanism
Fick's Law (for diffusion of gases)
mg = = - a dCg
Jg Dg
At dz
Fick's law assumes that gases are dilute and that there is equimolar counter diffusion of each gas.
a
Dg is the diffusion coefficient in air without soil and C g is concentration of gas.
What happens to Dag for soil?
Le
Le is the effective length

In soil, not air, the equation becomes
mg ∆Cg
= − Dag
Aet Le
where Ae is the effective pore area. The soil-air content, a, is
vol gas Ae Le
a= = or
total vol A L
aAL
Ae =
Le
Thus
mg = - a LDag ∆Cg
At Le Le
Multiplying top & bottom by L gives Jg = - a

L2 Dag ∆Cg
Le2 L
2
 L
Let D = a 
s
g  Dag
 Le 
∆ Cg
Thus Jg = - Dsg or Jg = - Dsg dCg
L dz
s
Dg is the apparent diffusion coefficient for soil or soil-gas diffusivity
Self diffusion coefficient is for a gas into itself
Mutual (or binary) diffusion coefficient is for one gas diffusing into a different gas
2
 L
  is called the tortuosity factor
 Le 
For some cases Dsg = 0.66 a Dag (not too good when a is small)
Thus
2
L 2
cm soil
  = 0.66 2
Penman
 Le  cm air
Other Relationships
s 3/2 a
Dg = a Dg Marshall
s 4/3 a
Dg = a Dg Millington
Dg = γ a Dg
s µ a
Currie
10/3
sa a
D = 2 Dg
g Millington and Quirk
φ
iFGH a a IJK
2+3/ b
Dsg = d 3
2a100 + 0.04a100
100
D ag Moldrup et al. (1999)
where a100 is the soil-air content at a soil-water pressure head of –100 cm of water and b is the slope
of the Campbell water retention function. If b is not known, it can be estimated from the clay
fraction given by the following equation:
b = 13.5 CF + 3.5 where CF is the clay fraction.
Effect of temperature on Dg
n
 T2 
DT 2 = DT1 
 T1 
Where T is in degrees Kelvin. The value of n has been found to be about 1.72-1.75.
0.
5
Dgs/Dga Penman
Millington &
Quirk
0
0 0.5
Soil-air content (a)
Two relationships of soil gas diffusion coefficient to soil-air content.
The SWC dependent model is the one by Moldrup et al. (1999)

An apparatus for measuring the diffusion coefficient for soil
Diagram giving initial and boundary conditions
C=C0 t≥0
X=0
Soil
Core
C=C0 t=0
X=-L
C=Ci t=0
C=f(t) t›0
Diffusion
Chamber
X=-(L+a)
Position A
Soil
Core
Slide - Horizontal
Diffusion Chamber
Sample Port
Position B
Soil
Core
Diffusion Chamber
Sample Port
Method of measuring Dsg in lab
mg dC
- Jg = - = - Dsg g (flow down)
At dz
mg - mass of gas
Cg - concentration in chamber
dmg dC
- = - Dsg A g V - volume of chamber
dt dz
mg = Cg V
s
dC D A dCg
∴ g =+ g
dt V dz
Co - Concentration of tracer gas
dCg Cg - Co
≅ at the top of the core
dz -L
L - Length of soil core
s
dCg D A g
=- (Cg - Co )
dt VL
Rearranging
dCg  Dsg A 
=-  dt and integrating
Cg - Co  VL 
cg t
dCg  Ds A 
∫ Cg - Co
= -  g  ∫ dt
 VL  o
ci
Where Ci is initial concentration in chamber at t=0
Cg  Dsg A  t
ln (Cg − C 0 ) Ci = -  t0
 VL 
 Ds A 
ln (Cg - Co ) - ln (Ci - Co ) = -  g  t
 VL 
 Cg - Co   Dsg A 
ln  =- t
 Ci - Co   VL 
If Ci = 0
 C - C   Ds A 
ln  o g  = -  g  t
 Co   VL 
dCg Cg - Co
Equation not valid for small times because ≠
dz -L
Also, equation does not take into account change in storage of gas in soil core.
-0.02
-0.04
ln [(Cg - Co)/(Ci - Co)]
-0.06
-0.08
-0.10
0 0.5 1.0
Time (hours)
A plot of ln [(Cg - Co)/(Ci - Co)] vs. time using hypothetical data from a soil core with values of a=
0.1 m3 m-3, L = 76 mm, A = 4540 mm2, and V = 0.5 L.
Diffusion equations
With concentration on fluid basis
Steady State
s dCg
J g = - Dg
dz
Cg is concentration on fluid basis and units are g gas/cm3 soil air
3
g gas s g gas/ cm air
2
= - D g
cm soil s cm soil
3
cm air
∴ Dsg =
cm soil s
Transient State
∆ storage = ∆ flux
∂ Cg ∂J
a =- g
∂t dz
∂ Cg 2
∂ Cg
a = Dsg
∂t ∂z 2
∂ Cg 2
∂ Cg
s
Dg
= Dm Dm =
∂t ∂z 2 a
2
soil
∴ Dm = cm
s
With concentration on soil basis use Cm
Steady State
dCm
J g = - Dm
dz
Cm - g gas/cm3 soil
Transient State
∂ Cm 2
∂ Cm
= Dm
∂t ∂z 2
2
g cm soil g
3
= 3 2
cm soil s s cm soil cm soil
Dissolution of gas in soil water and adsorption on soil
∂ Cg s ∂ Cg ∂ Sw
2
∂
a = Dg - - Ss
∂t ∂z 2
∂t ∂t
where Sw (g gas / cm3 soil) is amount of gas dissolved in water and Ss (g gas / cm3 soil) is amount of
gas adsorbed to soil solids.
The relationships between gas phase and water phase concentrations are
Cg = K H Sw / θv or Sw = Cg θv / K H
where K H is the "dimensionless" Henry's coefficient (cm3 water/cm3 air).
The relationship between the gas dissolved in the liquid phase and that in the sorbed phase is
Ss / ρb = Kd Sw / θv
where Kd (cm3 water /g soil) is the liquid/soil partition coefficient. Substituting Sw from the
equation above gives
Ss = Kd ρb Cg / K H
Taking the derivatives of S w and S s with respect to time and substituting into the original equation
gives
 θ v K dρ b  ∂ Cg 2
s ∂ Cg
 a + + = D
K H  ∂t
g
 KH ∂z 2
Dividing both sides by a gives
 θv K d ρ b  ∂ Cg 2
∂ Cg
1 +
 aK + = D
aK H  ∂t
m
 H ∂z 2
or
∂ Cg Dm ∂ 2 Cg
=
∂t R ∂z 2
where Dm = Dsg / a and R is the retardation coefficient given by
θv Kρ
R =1+ + d b
aK H aK H
Consumption or Production of Gases
- O2 consumed
- CO2 produced
- some gases adsorbed
- some gases react
∂ Cg 2
s ∂ Cg
a = Dg + r g (z, t)
∂t ∂z 2
r g (z, t) is sink or source terms to take consumption or production into account

A steady-state solution for gas diffusion and consumption

dCg
Jg = − D sg
dz
For O2
∂Cg ∂ 2 Cg
= Dm 2 − S( z, t )
∂t ∂z
where S(z,t) = rg(z,t)/a and rg is the gas reaction rate.
Assume
S(z, t) = α, α is a constant O2 consumption rate
∂ Cg
assume steady state, =0
∂t
d Cg α
2 2
d Cg
Dm 2
= α, 2
=
dz dz Dm
Integrate once with respect to z
∫d C ∫ α dCg α
2
g
2
dz = dz, = z + c1
dz Dm dz Dm
where c1 is a constant of integration.

Integrate again with respect to z
∫ ddzC g
dz = ∫ α
∫
zdz + c1 dz
Dm
to give
α 2
Cg = z + c1 z + c 2
2 Dm
where c2 is an additional constant of integration.
At z = 0, Cg = Co. Therefore, Co = C2, and
α 2
Cg = z + c1 z + Co
2 Dm
Assume we have a finite column with a closed bottom or a water table at depth L, flux at
depth L = 0 or dCg/dz = 0. Substituting dCg/dz = 0 in equation determined after first
integration gives
α
0= L + c1
Dm
α
c1 = -
L
Dm
α 2 αL
Cg = z - z + Co
2 Dm Dm
Oxygen profiles in soils as related to degree of biological activity and the soil gaseous
diffusion coefficient.
Curve Degree of Activity Dgs/Dga

(liters/m3 day)
1 10 0.06
2 5 0.06
3 10 0.25
4 5 0.25
Soil 1
Depth 2
(m)
3
4
1
1 2
5 Oxygen (%) 1
Aeration - Effects on Plants
1. O2 needed for root respiration - critical values of flux
2. Good aeration is essential for maximum H2O absorption.
Sudden reduction of O2 will cause growing plant to wilt.
3. CO2 retards uptake of nutrients.
Reduction follows K>N>P>Ca>Mg
4. CO2 & H2O form carbonic acid which increases the solubility
of many soil minerals. Some ions may become toxic to plants
5. Growth of roots limited by either lack of O2 or buildup of CO2
6. O2 needs increase with temperature
7. O2 needs increase as soil-water pressure head increases
- physical process-meaning at lower air content, gradients must be increased
8. Rate of O2 flux (supply) and CO2 removal is most important
Diffusion to plant roots
- O2 must diffuse through water films to reach root
- Mechanism simulated by measuring O2 diffusion to a

microelectrode
It This is the oxygen diffusion rate (ODR)

Jg =
n * F′A
It is current (amps) in time t

n* = 4 for O2 molecules
F' is the Faraday constant = 96,500 coulombs
A is the surface area of the electrode
s
Dg cannot be determined.
Several figures related to aeration follow:
Oxygen diffusion rates at a given soil depth as a function of depth of water table. (Williamson and
van Schilfgaarde, 1965).
Above figure from Glinski and Stepniewski (1983)

Other Diffusion Processes
-Flooded soil or sediments
• O2 diffusion
• NH3 volatilization
• Solute diffusion
A diagram showing diffusion processes in flooded soil (Reddy et al.)

- Denitrification
Aggregate or anoxic pocket or "hot spot"
O2
Anoxic
Zone
NO3
N2O or
N2
Also
- Diffusion of radon gas from soil into dwellings
- Volatilization of pesticides or volatile organics from soil
__________________________________________________
Stagnant Air Layer
________________________________________________
Soil Surface
Soil + Pesticide
Pesticide
Diagrams concerning volatile organic chemical transport processes follow:

Water Vapor Movement
d ρv
J wv = - Dv
dz
ρv- vapor density in gaseous phase

Dv - diffusion coefficient for water vapor in soil corrected for tortuosity (See book)
Vapor density gradients caused by
1. Differences in matric potential and solute potential

2. Temperature differences
Vapor density, Dv, in grams of vapor per cubic cm of pore space (g/cm3) at various temperatures and
at two soil-water potentials.
Temperature (C) Water Potential

-0.1 bar (-9.8 kPa) -15 bars (-1500 kPa)
15 12.83 x 10-6 12.70 x 10-6
18 15.37 x 10-6 15.22 x 10-6
20 17.30 x 10-6 17.13 x 10-6
21 18.34 x 10-6 18.16 x 10-6
22 19.43 x 10-6 19.24 x 10-6
23 20.58 x 10-6 20.37 x 10-6
24 21.78 x 10-6 21.56 x 10-6
25 23.05 x 10-6 22.82 x 10-6
30 30.38 x 10-6 30.08 x 10-6
35 39.63 x 10-6 39.23 x 10-6
at - 0.1 bars have 100% relative humidity

at - 15 bars have 98.98% relative humidity
... Differences in water potential will have little effect on vapor transport
Temperature differences have the much larger effect, but still little difference in effects of
water potential over the range between - 0.1 and - 15 bars at different temperatures
Appreciable vapor phase water flow will occur in the field surface soil due to the
development of large vapor density gradients

Chapter 7 - Gas Flow: Important Soil Gases

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SSC 107, Fall 2002 – Chapter 7 Page 7-1

Chapter 7 - Gas Flow

Important Soil Gases

O2 CO2 H2S NH3 N2 N2O NO CxHy

An example of diffusion processes related to contaminants in the vadose zone

Mechanisms for transfer of gases

1. Mass flow in vapor phase

a. Barometric pressure changes

2. Mass flow in dissolved (liquid) phase

a. Movement with water

3. Diffusion in liquid phase

a. 103 - 104 smaller than diffusion in vapor phase

4. Diffusion in vapor phase

a. Probably main mechanism

Fick's Law (for diffusion of gases)

What happens to Dag for soil?

Le is the effective length

In soil, not air, the equation becomes

where Ae is the effective pore area. The soil-air content, a, is

Multiplying top & bottom by L gives Jg = - a

Self diffusion coefficient is for a gas into itself

b = 13.5 CF + 3.5 where CF is the clay fraction.

Two relationships of soil gas diffusion coefficient to soil-air content.

The SWC dependent model is the one by Moldrup et al. (1999)

An apparatus for measuring the diffusion coefficient for soil

Diagram giving initial and boundary conditions

Method of measuring Dsg in lab

Where Ci is initial concentration in chamber at t=0

Cg is concentration on fluid basis and units are g gas/cm3 soil air

With concentration on soil basis use Cm

Dissolution of gas in soil water and adsorption on soil

where K H is the "dimensionless" Henry's coefficient (cm3 water/cm3 air).

Dividing both sides by a gives

where Dm = Dsg / a and R is the retardation coefficient given by

Consumption or Production of Gases

- some gases adsorbed

- some gases react

r g (z, t) is sink or source terms to take consumption or production into account

A steady-state solution for gas diffusion and consumption

where S(z,t) = rg(z,t)/a and rg is the gas reaction rate.

S(z, t) = α, α is a constant O2 consumption rate

Integrate once with respect to z

where c1 is a constant of integration.

Integrate again with respect to z

where c2 is an additional constant of integration.

At z = 0, Cg = Co. Therefore, Co = C2, and

Curve Degree of Activity Dgs/Dga

Aeration - Effects on Plants

1. O2 needed for root respiration - critical values of flux

2. Good aeration is essential for maximum H2O absorption.

Sudden reduction of O2 will cause growing plant to wilt.

3. CO2 retards uptake of nutrients.

Reduction follows K>N>P>Ca>Mg

5. Growth of roots limited by either lack of O2 or buildup of CO2

6. O2 needs increase with temperature

7. O2 needs increase as soil-water pressure head increases

- physical process-meaning at lower air content, gradients must be increased

8. Rate of O2 flux (supply) and CO2 removal is most important

Diffusion to plant roots

- O2 must diffuse through water films to reach root

- Mechanism simulated by measuring O2 diffusion to a

It This is the oxygen diffusion rate (ODR)

It is current (amps) in time t