AMMONIA TRANSFER ACROSS THE INTERFACE

1. Rate equation

The physical process of ammonia transfer across a water surface in contact with the atmosphere is
described by the simple reaction:

NH 3 (aq ) ↔ NH 3 (g ) (1)

This process tends to restore the thermodynamical equilibrium which is reached when the chemical
potential (or fugacity) of ammonia is equal in both phases.

An introduction to the modeling of gas exchange with the atmosphere is given in the section devoted to
oxygen transfer across the interface. However, the behavior of ammonia is different from that of
oxygen, because (1) it is a fairly soluble species and (2) it is involved in a very fast equilibrium with
ammonium in the water phase. As a consequence, two questions deserve a special attention when
dealing with ammonia exchange. The first one concerns the relative importance of the air and water
boundary layers in controlling the overall transfer velocity; the second one deals with the effect of the
NH3 / NH4+ equilibrium on the transfer rate, a mechanism known as the “diffusion enhancement”.

A general expression for the rate of gas transfer across the interface is given by the solution of the
following set of equations:

F = − v w (C w − C w , i ) = − v a (C a ,i − C a ) (2)
C a ,i = K '
H .C w , i (3)

where Cw and Ca respectively refer to the bulk water and air concentrations of the gas, Cw,i and Ca,i
are the equilibrium concentrations at the water and air side of the interface , and vw and va are the
piston velocities, respectively in the water and in the air boundary layers. ( ( v w ) −−1 and ( v a ) −−1 are also
known as the transfer resistances of the layers). K 'H is the dimensionless Henry’s law constant for
the considered gas. Note that the flux is taken positive when the gas is supplied from the atmosphere
to the water.

Substitution of Ca,i in equation (2) by its expression from equation (3) and elimination of Cw,i leads to:

Ca
F = − v tot (C w − ) (4)
K 'H

with:

1 1 1
= + (5)
v tot vw v a K 'H

The total resistance to gas transfer ( v tot ) −−1 can thus be considered as the sum of two resistances in
series, one for each boundary layer.

In the case of ammonia, equations (4) and (5) can be re-written as:
 p NH 3
tot ([ NH3 ] −
FNH 3 = − v NH )
3
(6)
KH

1 1 1
= + (7)
NH 3 NH 3 NH 3
v tot v w v a K 'H

in which [NH3] is the bulk concentration of ammonia in the water phase; p NH 3 is the partial pressure
of ammonia in the bulk of the gas phase; vtot, vw and va respectively refer the total, water and air piston
velocities of ammonia; KH is the Henry’s law constant for ammoniac and K 'H the corresponding
dimensionless constant.

In a 1-D model, the flux must be formulated per unit volume V and Eq.6 must be transformed
accordingly. This leads to:

S 1
[FNH 3 ]V = FNH 3 = FNH 3 (8)
V h

where [F]V is the flux per unit volume, S [m2] the surface area of V in contact with the atmosphere
and h the water depth [m].

2. Henry’s Law constants for ammonia

In the following, we use the Henry’s Law constant defined as:

pa
KH = (9)
Cw

where pa is the partial pressure of the compound in the air phase [atm] in equilibrium with the
concentration Cw [mole.m-3] of this compound in the water. The units of KH are thus atm.m3.mol-1.

When the concentration in the gas phase is expressed in unit of concentration [mole.m-3] instead of
pressure, the resulting constant K 'H (the so-called dimensionless Henry’s Law constant) is expressed
as:

Ca
K 'H = (10)
Cw

If the gas is considered as ideal, conversion between both constants is straightforward:

KH
K 'H = (11)
RT

where T is the absolute temperature [K] and R the universal gas constant (8.206.10-5 m3.atm.mol-1.K-
1
).
For NH3, the values at 25°C are:

KH = 1.75 10-5 atm.m3.mole -1 (0.0175 atm.l.mole -1)

K 'H = 7.15 10-4

Temperature dependence:

Based on data from an exhaustive literature review (Data from NIST Standard Reference Database),
Sander(1999) proposes the following temperature function:

4200
ln K H = − + 3 .133 (12)
T

Salinity dependence:

The effect of ionic strength on the value of the Henry’s Law constant, linked to the increase of the
activity coefficients, is not greater than 10% over the salinity range. This effect will be ignored at this
stage.

3. Piston velocity

Diffusion enhancement

Enhanced diffusivity in the water phase appears when two species X and Y are reacting in a very fast
inter-conversion process but only one can cross the air-water interface. This is obviously the case for
the NH3 / NH4+ equilibrium.

In the general case, the equilibrium condition can be expressed by a relation of the form:

[Y ] = K [X ] (13)

where X refers to the species that cross the interface. In the computation of the water piston velocity
(see below), the molecular diffusion coefficient Dw of the dissolved species has then to be replaced by
the “enhanced diffusion coefficient D 'w ” which is given by:

D 'w = D w (1 + K) (14)

(For a detailed demonstration, see for example Schwartzenbach et al. 1993). Note that this is only true
if both species X and Y exhibit a very close diffusion coefficient in water.

In the case of ammonia, the relation (13) is:

 [NH ] = [ NH ] [H ]
++
++ 3
4 (15)
K 'NH ++
4

and the enhanced diffusion coefficient is equal to:



D 'w = D w 1 +
[H ++ ]  (16)

 K ' ++ 
 NH 4 

Depending on the temperature and the salinity, the pK’ of ammonia will vary between 9 and 10 (for
details, see ammonia dissociation), so that under normal pH conditions (<8), the diffusivity will at least
be enhanced by a factor of 10.

Overall piston velocity

As shown before, the overall piston velocity vtot can be expressed as:

1 1 1 1 1
= + = + (17)
v NH
tot
3
v NH
w
3
v NH
a
3
K 'H v NH
w
3
v 'aNH 3

where vw and va respectively refer to the piston velocity in the liquid (water) and in the gas (air) layers.
In order to assess the relative importance of the air and water boundary layers on the ammonia
transfer, we will now evaluate the value of the resistance ratio Ra/w defined as:

1
v 'a v
Ra/w = = w (18)
1 v 'a
vw

Piston velocity in the air phase

The velocity for ammonia can be deduced from the velocity of a reference gas (i.e. water vapor) by
use of the following relationship:

α
 D NH 3 
v aNH 3 = v Ha 2 O  a  (19)
 D H2O 
 a 

where the Da′s refer to the molecular diffusion coefficients in air and α is close to 0.66
(Schwartzenbach et al., 1993).

The diffusion coefficients of ammonia can be linked to the diffusion coefficient of water by:

0. 5
 mol. weight H 2 O 
D aNH 3 = D Ha 2 O   (20)
 mol. weight NH 
 3 

Combining these last two expressions leads to:

 0 .33
 mol. weight H 2 O 
v NH 3
=v H2O   (21)
a a
 mol. weight NH 
 3 

0 .33
 18 
v NH 3
a =v H2O
a
  = 1 .02 v Ha 2O (22)
 17 

and:

v 'aNH 3 = K 'H v NH
a
3
= 1.02 K 'H v Ha 2 O (23)

Using the formulation proposed by Schwartzenbach et al. (1993) for the piston velocity of H2O in the
air phase as a function of wind velocity:

v Ha 2 O = 10 −−2 (0.2 u 10 + 0.3) (24)

we obtain:

v 'aNH 3 = 1.02 10 −−2 K 'H (0 .2 u 10 + 0.3) (25)

where u10 is the wind speed (in m.s-1) measured at a height of 10 m above the water surface and the
piston velocity is given in m.s-1.

At 25°C, K 'H = 7.15 10 −−4 and thus:

v 'aNH 3 = 7.3 10 −−6 (0 .2 u 10 + 0.3) (26)

Piston velocity in the water:

The piston velocity for ammonia can be estimated from the velocity of a reference gas (i.e. oxygen)
according to the following relationship:

β
 D 'wNH 3 
v NH 3
=v O2   (27)
w w
 D O2 
 w 

where D 'wNH 3 refers to the enhanced diffusion coefficient of ammonia in water and β is close to 0.57
(Holmen and Liss, 1984).

The enhanced diffusion coefficient for ammonia is estimated from the diffusion coefficient of oxygen
by:


[H ++ ] 
0. 5
 mol. weight O 2  
D 'wNH 3 = D Ow 2  
 1 +  (28)
 mol. weight NH   K 'NH ++ 
 3   4
Combining these last two expressions leads to:

0 .57

[H ++ ] 

0 .285
 mol. weight O 2  
v NH 3
=v  O2 
1 + '  (29)
w
 mol. weight NH
w
  K ++ 
 3   NH 4 

Recalling that the enhancement factor is at least equal to 10, the lowest value of the ammonia piston
velocity in water will be:

0 .285
 32 
v NH 3
w = v  
O2
w (10) 0. 57 = 4.45 vOw2 (30)
 17 

A formulation for the piston velocity of oxygen as a function of the wind speed (Wanninkhof, 1992) is
given in the section devoted to oxygen transfer across the interface:

1
−−
 1   Sc 
= K u 2  
2
v Ow 2 (31)
 3.6 10 5  10  660 
 

where u10 is the wind speed (in m.s-1) measured at a height of 10 m above the water surface. For
oxygen, the Schmidt number Sc is equal to 590 at 20° and a salinity of 35. The coefficient K is
comprised between 0.31 and 0.39. Using this formulation we obtain:

1
−−
 1   590 
= 4.45   0.31 u 2  
2
v NH3
= 9.1 10 −−7 u 10
2 (32)
w
 3 .6 10 5  10
 660 
 

Note that we neglect here the effect of the current velocity: this allows us to compare the relative
importance of the resistance in the air and water boundary layers under various wind speed conditions.

Value of the resistance ratio:

The table in annex gives the piston velocity in air and in water, and the resistance ratio Ra/w, for various
values of the wind speed. These results indicate that, under normal pH conditions (pH < 8) and under
moderate to high wind conditions, most of the transfer resistance (60 to 90%) will take place in the air
boundary layer. Neglecting the transfer resistance in the water boundary layer will thus introduce an
error lower than 40%. A larger error occurs at low wind speed, but the contribution of the water
velocity is then important: it increases vw, and thus increases the value of the resistance ratio.

Accordingly, we propose to neglect the transfer resistance in the water boundary layer, although using
the complete (2-layers) model does not add a considerable difficulty and could be done at a later stage.
Also recall that the error in the estimation of both va and vw from the value of u10 is probably larger
than 20%.

4. Partial pressure of ammonia in the atmosphere

NH3 is the only gaseous neutralizing substance for acidic compounds in the atmosphere. It reacts with
H2SO4 and HNO3 either in aerosol particles or in cloud, fog and precipitation waters, so that the
concentration of free atmospheric ammonia is usually quite low. NH3 concentrations in the surface air
over the continents are typically between 0.2 and 2 ppb. (Meszaros, 1992). According to Pitts (1986),
NH3 concentrations range from 1-10 ppb in rural and moderately polluted areas, to 10-100 ppb in
heavily polluted zones.

Let us take 2 ppb (2 10-9 atm) as an average value for atmospheric concentration over the Scheldt. At
a temperature of 10°C, the term pa / KH is equal to 2.4 10-7 mole/l. Taking a pH equal to 7 and a
pK 'NH ++ equal to 9, this corresponds to a NH4+ water concentration of 2.410-5 mole/l (24 µM), which is
4

only one order of magnitude lower than the NH4+ concentrations observed in the upper reach of the
estuary (100 to 500 µM).

5. Model entries for computing the ammonia transfer across the interface

1. Number of species: 1
2. Number of kinetic reactions: 1
3. Number of equilibrium conditions: 0
4. Variables: [ NH 3 ]
5. Reaction:
R1: NH 3 (aq) ↔ NH 3 (g)
6. Rate:
1 p NH 3
FNH 3 = − v 'aNH 3 ([ NH 3 ] − )
h KH
v 'aNH 3 = 1.02 10−−2 K 'H (0.2 u 10 + 0.3)

7. Model parameters: KH and K 'H (depend on temperature); p NH 3 (partial pressure of ammonia in

air); u10 (wind speed at 10 m height); h (water depth) is calculated by the hydrodynamic model.

References

Finlayson-Pitts, B.J. and Pitts, J.N., 1986. Atmospheric chemistry: Fundamentals and experimental
techniques. J. Wiley, 379 pp.

Holmen K. and Liss, P., 1984. Models for air-water gas transfer: an experimental investigation. Tellus,
36B, 92-100.

Meszaros, E., 1992. Occurence of atmospheric acidity. In: Radolevic M. and Harrison, R.M. eds,
Atmospheric acidity: Sources, consequences and abatement, 1-37. Elsevier.

Sander, R.,1999. Compilation of Henry's Law constants for inorganic and organic species of potential
importance in environmental chemistry (Version 3).
http://www.mpch-mainz.mpg.de/~sander/res/henry.html

Schwartzenbach, R.P., Gschwend, P.M. and Imboden, D.M. 1993. Environmental organic Chemistry.
J. Wiley, 681 pp.
 Annex: resistance ratio vs wind speed

Wind speed v'a vw Ra-w Error

m/s m/s m/s %
1 3.7E-06 9.1E-07 0.2 -401
2 5.1E-04 3.6E-04 0.7 -140
3 6.6E-04 8.2E-04 1.2 -80
4 8.0E-04 1.5E-03 1.8 -55
5 9.5E-04 2.3E-03 2.4 -42
6 1.1E-03 3.3E-03 3.0 -33
7 1.2E-03 4.5E-03 3.6 -28
8 1.4E-03 5.8E-03 4.2 -24
9 1.5E-03 7.4E-03 4.8 -21
10 1.7E-03 9.1E-03 5.4 -18
11 1.8E-03 1.1E-02 6.0 -17
12 2.0E-03 1.3E-02 6.6 -15
13 2.1E-03 1.5E-02 7.3 -14
14 2.3E-03 1.8E-02 7.9 -13
15 2.4E-03 2.0E-02 8.5 -12
16 2.6E-03 2.3E-02 9.1 -11
17 2.7E-03 2.6E-02 9.7 -10
18 2.8E-03 2.9E-02 10.4 -10
19 3.0E-03 3.3E-02 11.0 -9
20 3.1E-03 3.6E-02 11.6 -9