5 Gas Exchange

Air-Water Gas Exchange of Chemicals
terry.bidleman@ec.gc.ca
Centre for Atmospheric Research Experiments

Science & Technology Branch, Environment Canada
Photo: Thule Bay, Alaska

Jim Milne, DRDC
Why?
Air-Water Gas Exchange of Persistent
¾ 71% of earth’s surface is water. Cl
Organic Pollutants (POPs) Cl Cl
¾ Gas phase important for many
semivolatile chemicals
terry.bidleman@ec.gc.ca Cl Cl
¾ Major pathway of transport for Cl
many compounds, especially
in oceans and large lakes.
α-hexachlorocyclohexane (α-HCH) Cl
Cl Cl
Cl Cl
Cl
Centre for Atmospheric
Photo: Lake Superior Research Experiments
Science
Liisa & Technology
Jantunen, Branch, Environment Canada
Environ. Canada
Henry’s Law Constant
H = p/CW
P = partial pressure, Pa
CW = water concentration, mol/m3
KAW = CA/CW = air-water partition coefficient = H/RT
Sometimes KAW is called the

dimensionless Henry’s Law constant, H’
Getting the Henry’s Law Constant
1. Calculate from saturation vapour pressure and solubility.
Note: either liquid-phase or solid-phase properties can be
used, because melting point corrections cancel, but don’t
mix!
H = poL/SoL or poS/SoS
2. Calculate from octanol-water (KOW) and octanol-air (KOA)

partition coefficients:
gas
phase
KAW = KOW/KOA KAW KOA
aqueous KOW organic

dissolved dissolved
phase phase
Getting the Henry’s Law Constant
3. Measure directly; common method is bubble stripping.
pre-saturator
column
air
outlet
air
Constant insulation
Temperature
water bath bubbling
chamber
N2 constant
temperature
water
outlet
Gas stripping relationship
Vt lnCt/Co = –(HG/RT)t
Ct and Co are solution

concentrations at time = t
and time = 0, hours.
Vt lnCt/Co
Slope = –HG/RT
G = gas flow, m3/h
Vt = solution volume (m3) at
time = t
H = Pa m3/mol
time
L. Jantunen & T. Bidleman, Chemosphere 62: 1689-1696 (2006);

L. Sahsuvar et al., Atmos. Environ. 37: 983-992 (2003)
Problem with the gas stripping method:
¾ HLCs biased too high by adsorption to bubble-air interface
¾ More serious for highly hydrophobic (low solubility) chemicals
Y.D. Lei et al., J. Chem. Eng. Data (2006)

¾ Enhancement factors (EF) for
alcohols of different carbon
chain length (nc).
¾ EF expresses the extent to
which KAW values are elevated
due to adsorption to the
air-bubble interface.
Y.D. Lei et al.,

J. Chem. Eng. Data (2006)
Temperature relationships for vapour pressure,
solubility and Henry’s law constant
Ln poL = −ΔHvap/RT + bvap

From: H = poL/SoL
Ln SoL = −ΔHsol/RT + bsol ΔHhlc = ΔHvap−ΔHsol
Ln H = −ΔHhlc/RT + bhlc
Ln SoL
Ln poL
Ln H
1/T 1/T 1/T
The Henry’s law constant decreases with temperature
At constant partial pressure, gases are more soluble
at lower temperatures.
Apparent to anyone with a fish tank!
Solubility of oxygen in water
partial pressure = 0.21 atm (2.1 x 104 Pa)
Temperature, oC Solubility,
mL O2/L water
5 8.90
15 7.05
25 5.77
Salting Out (Setchenow Equation)
¾ Most organic chemicals are less soluble in salt water

than in fresh water.
¾ Since H = po/So, adding salt raises H.
¾ Important consideration for gas exchange in oceans.
¾ Change in solubility is predictable from
the Setchenow Equation
Log(Sosalt /So) = –KSCsalt
¾ So and Sosalt are solubilities in pure water and

salt solution of concentration Csalt (M).
Salting Out (Setchenow Equation)
Log(Sosalt/So) = –KSCsalt
¾ The Setchenow coefficient, KS varies with the

chemical and the salt.
¾ For PCBs in seawater, KS = 0.2 – 0.3
¾ What is Sosalt/So? Seawater is ~0.5 M NaCl.
Log(Sosalt/So) = –0.25(0.5) = -0.125

Sosalt/So = 0.75, or a 25% decrease
Accordingly, H should increase by 25%
Finding the Net Exchange Direction
¾ Gas exchange is a two-way street.

¾ Deposition (invasion) and volatilisation (evasion)
occur simultaneously.
¾ Which pathway dominates (net exchange)?
Using measured CW and CA, calculate (CW/CA)meas

Compare to CW/CA at equilibrium (1/KAW = RT/H)
If (CW/CA)meas = 1/KAW, no net exchange (equilibrium)
If (CW/CA)meas is >1/KAW, net volatilisation
If (CW/CA)meas is <1/KAW, net deposition
¾ The pesticide toxaphene was heavily applied in the southern
U.S. during the 1960s and 70s. Use was stopped in 1986.
¾ During the usage years, toxaphene was atmospherically
transported northward and deposited into Lake Superior,
resulting in high concentrations in the water.
¾ Today, air concentrations of toxaphene have decreased and
the pesticide is revolatilising from the lake.
¾ For details of this story, see papers by:
D. Swackhamer et al., Environ. Sci. Technol. 33: 3864-3872 (1999)

R. James et al., Environ. Sci. Technol. 35: 3653-3660 (2001)
L. Jantunen & T. Bidleman, Environ. Toxicol. Chem. 22: 1229-1237(2003)
Toxaphene concentrations in Lake Superior water and air in 1996
were 918 ng/m3 (CW) and 0.020 ng/m3 (CA). The Henry’s law
constant is1,2:
Log H (Pa m3/mol) = 10.42 – 3209/T
What is the net exchange direction of toxaphene at 22oC?
1. (CW/CA)meas = 918/0.02 = 4.6 x 104

2. Log H = 10.42 − 3209/295 = −0.458, H = 0.348 Pa m3/mol
3. 1/KAW = RT/H = (8.314 x 295)/0.348 = 7.0 x 103
4. Since (CW/CA)meas is >1/KAW (step 1 > step 3)
5. Water is oversaturated, net volatilisation
1. Jantunen, L., Bidleman, T. Chemosphere, Global Change Science 2: 225-231 (2000);
2. Jantunen, L., Bidleman, T. Environ. Toxicol. Chem. 22: 1229-1237 (2003)
Gas Exchange – Fugacity Approach1-3
¾ Fugacity (unit: Pa). For most environmental purposes
consider fugacity synonymous with partial pressure.
¾ Describes the “escaping tendency” of the chemical.
¾ Systems in equilibrium have equal fugacities.
¾ Fugacity in air:
fA = (n/V)RT = CART (ideal gas law)

¾ Fugacity in water:
fW = CWH (recall that H = p/CW)

where CA and CW have units mol/m3
1. Mackay, D. Environ. Sci. Technol. 13: 1218 (1979); 2. Mackay, D., Paterson, S.
Ibid. 15: 1006-1014 (1981); 3. Ibid. 16: 654A-660A (1982).
Toxaphene Example – Fugacity Approach
fA = [(2.0 x 10-11 g/m3)/414 g/mol](8.314 Pa m3/mol K)(295 K)

= 1.18 x 10-10 Pa
fW = [(9.18 x 10-7 g/m3)/414 g/mol](0.348 Pa m3/mol) =

= 7.72 x 10-10 Pa
Since fW > fA, toxaphene is undergoing net volatilisation
Another way to consider this is by calculating fW/fA
fW/fA = CWH/CART
In this example, fW/fA = 7.72 x 10-10/1.18 x 10-10 = 6.5

Fugacity Decision Rules
fW/fA > 1: net volatilisation

fW/fA = 1: equilibrium (no net exchange)
fW/fA < 1: net deposition
In the previous example, we assumed the same air and water
temperature (22oC). What if the temperatures are different1?
fW/fA = CWH/CARTA
Henry’s law constant at air temperature

water temperature
1. See: Wania, F. et al., Environ. Pollut. 102: 3-23 (1998)

Summary of steps to calculate gas exchange direction
1. Measure CA and CW. CA is for the gas phase only and CW is for the
dissolved phase only (no particles, colloids). Experimental challenges!
2. Calculate H (and KAW) for the chemical at the water temperature.
3. Calculate (CW/CA)meas
4. Compare with RT/H = 1/KAW.

(CW/CA)meas = 1/KAW: equilibrium
(CW/CA)meas > 1/KAW: net volatilisation
(CA/CW)meas < 1/KAW: net deposition
4. Compare with RT/H = 1/KAW.

(CW/CA)meas = 1/KAW: equilibrium
(CW/CA)meas > 1/KAW: net volatilisation
(CA/CW)meas < 1/KAW: net deposition
5. Or, calculate fW/fA = CWH/CARTA

fW/fA = 1: equilibrium
fW/fA > 1: net volatilisation
fW/fA < 1: net deposition
Two-Film Model of Gas Exchange Rates1,2
CA bulk air:
turbulence
air film:
ZA
diffusion
CA,S
CW,S
water film:
diffusion ZW
Equilibrium of surface concentrations:

bulk water:
H/RT = CA.S/CW,S CW turbulence
1. Whitman, W. Chem. Metal Eng. 29, 146-150 (1923)

2. Liss, P., Slater, P. Nature 247: 181-184 (1974)
Diffusion through the air and water thin films
limits the gas exchange rate
Fick’s first law: Flux = k • dC/dZ
Flux (mol/m2 h) = mass transfer coefficient x conc. Gradient
Concentration gradients are assumed to be linear
Flux through the air (gas) film: FA = kG(CA – CA,S)

Flux through the water (liquid) film: FW = kL(CW,S − CW)
Flux (mol/m2 h) = mass transfer coefficient x conc. gradient

bulk

interface

mass transfer coefficients

for gas and liquid films
These equations are set up such that deposition flux

is positive (CA > CA,S and CW,S > CW).
¾ The above equations are not useful in this form, because

we don’t know the interfacial concentrations.
¾ However, we assume that the interfacial concentrations
are in equilibrium: H/RT = CA,S/CW,S
¾ Substituting this into the above equations, and assuming
steady state (FA = FW) leads to the next relationship:
Flux (F) = KOL(CART/H − CW)
water concentration actual
in equilibrium with air water concentration
Checking units: KOL is m/h, CA and CW are mol/m3 and

RT/H is dimensionless. Thus, F has units mol/m2 h
To repeat, this equation is set up such that deposition is positive

and volatilisation is negative. This is consistent with the convention
used in the Great Lakes Integrated Atmospheric Deposition Network
(IADN). Some papers define fluxes with the opposite sign
(i.e., volatilisation positive)1,2.
1. Bidleman, T., McConnell, L. Sci. Total Environ. 159: 101-117 (1995).

2. Wania, F. et al., Environ. Pollut. 102: 3-23 (1998).
Flux (F) = KOL(CART/H − CW)
KOL is the overall mass transfer coefficient, which includes

resistances to transfer in both the water and air films:
1/KOL = 1/kL + RT/HkG
overall water film

resistance air film
resistance
resistance
Which resistance dominates?
Depends on relative magnitude of kL, kG and H.
Situation #1: Air film resistance dominates
Lindane, H = 0.24 Pa m3/mol at 25oC. Assume

kG = 15 m/h and kL = 0.02 m/h (more later about kG and kL).
1/KOL = 1/(0.02) + 8.31(298)/(0.24)(15)

1/KOL = 50 + 688 = 738
water film air film

resistance (7%) resistance (93%)
Here, diffusion across the air film limits lindane exchange and there is
essentially no concentration gradient across the water film
(Cw = CW,S)
CA bulk air:
turbulence
air film:
diffusion
CA,S
CW,S
Equilibrium of surface
concentrations: CW bulk water:
H/RT = CA.S/CW,S turbulence
Situation #2: Water film resistance dominates
Same calculations for PCB-52. Again, assume kG = 15

m/h and kL = 0.02 m/h. H = 32 Pa m3/mol at 25oC
1/KOL = 1/(0.02) + 8.31(298)/(32)(15)

1/KOL = 50 + 5.2 = 55.2
water film air film
Here, diffusion across the water film limits PCB-52 exchange and
there is essentially no concentration gradient across the air film
(CA = CA,S)
Equilibrium of surface
CA concentrations: bulk air:
H/RT = CA.S/CW,S turbulence
CA,S
CW,S
water film:
diffusion
bulk water:
CW turbulence
Intermediate situation: both films contribute
Same calculations for p,p’-DDT. Again, assume kG = 15

m/h and kL = 0.02 m/h. H = 1.1 Pa m3/mol at 25oC
1/KOL = 1/(0.02) + 8.31(298)/(1.1)(15)
1/KOL = 50 + 150 = 200
water film air film
More about kL and kG
k = D/Z
D = molecular diffusivity; Z = film thickness
Typically, kL and kG are measured for light gases, such as water vapour,
oxygen and carbon dioxide. Adjustments of these k-values for higher
molecular weight and lower diffusivity molecules (like PCBs, pesticides)
are made using relative diffusivities and Schmidt numbers.
D, cm2/s Sc medium
H20 0.256 0.60 air
CO2 0.164 0.94 air
CO2 1.77 x 10-5 559 water
PCB52 0.052 2.94 air
PCB52 4.27 x 10-6 2665 water
What’s a Schmidt Number?
Sc = ν/D
D = molecular diffusivity of the chemical, cm2/s
ν = kinematic viscosity of water = viscosity/density
= (g/cm s)/(g/cm3) = cm2/s
So, ν/D is dimensionless
There are models for calculating Schmidt numbers and diffusivities in air and water.
See references in papers dealing with gas exchange.
Mass transfer coefficients are influenced strongly by wind speed.
Many experimental and theoretical relationships have been given which
relate k-values to wind speed, diffusivity and Schmidt number (Sc)1-3.
Here are two:
kL (cm/h) = (0.45U101.64)(ScX/Sccarb. diox.)-0.5
kg (cm/s) = (0.2U10 + 0.3)(DX/Dwater vap.)0.61
Note the different units for kL and kG, which is the way they were
published! The units of U10 in these equations are m/s and D is cm2/s.
If you want flux in mol/m2 h, need KOL in m/h. Multiply above kL by 10-2
m/cm and kG by 10-2 m/cm x 3600 s/h.
1. Bidleman, T., McConnell, L. Sci. Total Environ. 159: 101-117 (1995)

2. Wania, F. et al., Environ. Pollut. 102: 3-23 (1998).
3. Hornbuckle, K. et al., Environ. Sci. Technol. 28: 1491-1504 (1994)
kL (cm/h) = (0.45U101.64)(ScX/Sccarb. diox.)-0.5
kg (cm/s) = (0.2U10 + 0.3)(DX/Dwater vap.)0.61
From the previous table:

Sc values in water: 2665 for PCB52 and 559 for CO2.
D values in air: 0.052 for PCB52 and 0.256 for water vapour.
For U10 = 4 m/s (14 km/h):
kL = 2 cm/h, kG = 0.42 cm/s

In common units: kL = 0.02 m/h, kG = 15 m/h
Others use different relationships for kL and kG.

These are based on molar volumes, or atomic diffusion volumes, of
the chemicals instead of D and Sc.
Results not much different from the previous equations.
For details, see the following references:
1. Jantunen, L., Bidleman, T. Environ. Toxicol. Chem. 22: 1229-1237 (2003)

Calculating flux using fugacity terminology
Flux = DOL(fA - fw)
DOL = KOL/H
Checking units:
¾ KOL has units m/h
¾ DOL has units (m/h)/(Pa m3/mol) = mol/Pa m2 h
¾ When multiplied by fugacity (Pa), the result is
flux in mol/m2 h
Completing the gas exchange calculation for PCB-52
Assume CW = 0.5 pg/L (= 500 pg/m3) and CA = 2 pg/m3
Assume lake temperature = 15oC
KAW = H/RT = 8.36 x 10-3
RT/H = 120
MW = 292 (in case you want flux in moles/m2h)
KL and KG are 0.02 and 15 m/s
KOL = 1/kL + RT/HkG

1/KOL = 1/0.02 + 120/15
1/KOL = 50 + 8 = 58 (note mainly liquid-phase resistance)
KOL = 0.017 m/s
Fnet = KOL(CART/H – CW)

Fnet = 0.017(2*120 – 500) = –4.4 pg/m2h volatilisation
Gas exchange calculation for PCB-52 – fugacity approach
CW = 500 pg/m3 = 1.71 x 10-12 mol/m3
CA = 2 pg/m3 = 6.85 x 10-15 mol/m3
KAW = H/RT = 8.36 x 10-3, H = 20 Pa m3/mol
MW = 292
KL and KG are 0.02 and 15 m/s
DOL = KOL/H = 0.017/20 = 8.4 x 10-4 mol/Pa m2h

fW = CWH = 1.71 x 10-12(20) = 3.42 x 10-11 Pa
fA = CART = 6.85 x 10-15(8.31)(288) = 1.64 x 10-11 Pa
Fnet = DOL(fA - fW)

Fnet = 8.4 x 10-4 (1.64 x 10-11 – 3.42 x 10-11) = –1.49 x 10-14 mol/m2h
Fnet = –1.49 x 10-14(292 g/mol)(1012 pg/g) = –4.4 pg/m2h volatilisation
Summary of steps to calculate gas exchange flux
1. Calculate kL and kG as functions of wind speed (U10),
diffusivity (D), Schmidt number (Sc) or other relationships.
Note that both D and Sc are functions of temperature.
2. Calculate KOL (or DOL) using:

DOL = KOL/H
2. Calculate KOL (or DOL) using:

DOL = KOL/H
3. Calculate net flux using one of these relationships:
Fnet = Fdep-Fvol = KOL(CART/H − CW)
Fnet = DOL(fA − fW)

You can also calculate individual air and water
fluxes by simply using the two parts of the flux equation:
Fdep = KOL(CART/H)
Fvol = KOL(−CW)
Similarly for the equation in fugacity format.

–8.5 pg/m2h volatilisation
4.1 pg/m2h deposition
–4.4 pg/m2h net
Why might you want to do this?

Net flux of –4.4 pg/m2h doesn’t seem like much…
Lake Superior is huge! surface area is 82,100 km2 = 8.21 x 1010 m2
–4.4 pg/m2h x 8760 h/y x 8.21 x 1010 m2 x 10-15 kg/pg = –3.1 kg/y
¾ PCB-52 is only one of many PCBs in
the lake.
¾ In 1992, Hornbuckle et al.1 estimated an

annual average net flux of –345 pg/m2h
for total PCBs from Lake Superior.
¾ Total net volatilisation of –248 kg

annually!

5 Gas Exchange

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

5 Gas Exchange

Uploaded by

Copyright:

Available Formats

Air-Water Gas Exchange of Chemicals

Centre for Atmospheric Research Experiments

Photo: Thule Bay, Alaska

Sometimes KAW is called the

2. Calculate from octanol-water (KOW) and octanol-air (KOA)

KAW = KOW/KOA KAW KOA

aqueous KOW organic

 Ct and Co are solution

L. Jantunen & T. Bidleman, Chemosphere 62: 1689-1696 (2006);

Y.D. Lei et al., J. Chem. Eng. Data (2006)

Y.D. Lei et al.,

Ln poL = −ΔHvap/RT + bvap

¾ Most organic chemicals are less soluble in salt water

Log(Sosalt /So) = –KSCsalt

¾ So and Sosalt are solubilities in pure water and

¾ The Setchenow coefficient, KS varies with the

Log(Sosalt/So) = –0.25(0.5) = -0.125

¾ Gas exchange is a two-way street.

 Using measured CW and CA, calculate (CW/CA)meas

 D. Swackhamer et al., Environ. Sci. Technol. 33: 3864-3872 (1999)

What is the net exchange direction of toxaphene at 22oC?

1. (CW/CA)meas = 918/0.02 = 4.6 x 104

¾ Describes the “escaping tendency” of the chemical.

¾ Systems in equilibrium have equal fugacities.

fA = (n/V)RT = CART (ideal gas law)

fW = CWH (recall that H = p/CW)

fA = [(2.0 x 10-11 g/m3)/414 g/mol](8.314 Pa m3/mol K)(295 K)

fW = [(9.18 x 10-7 g/m3)/414 g/mol](0.348 Pa m3/mol) =

Since fW > fA, toxaphene is undergoing net volatilisation

Another way to consider this is by calculating fW/fA

In this example, fW/fA = 7.72 x 10-10/1.18 x 10-10 = 6.5

fW/fA > 1: net volatilisation

Henry’s law constant at air temperature

1. See: Wania, F. et al., Environ. Pollut. 102: 3-23 (1998)

2. Calculate H (and KAW) for the chemical at the water temperature.

2. Calculate H (and KAW) for the chemical at the water temperature.

4. Compare with RT/H = 1/KAW.

2. Calculate H (and KAW) for the chemical at the water temperature.

4. Compare with RT/H = 1/KAW.

5. Or, calculate fW/fA = CWH/CARTA

Equilibrium of surface concentrations:

1. Whitman, W. Chem. Metal Eng. 29, 146-150 (1923)

Fick’s first law: Flux = k • dC/dZ

Flux (mol/m2 h) = mass transfer coefficient x conc. Gradient

Concentration gradients are assumed to be linear

Flux through the air (gas) film: FA = kG(CA – CA,S)

Flux (mol/m2 h) = mass transfer coefficient x conc. gradient

Flux through the air (gas) film: FA = kG(CA – CA,S)

Flux (mol/m2 h) = mass transfer coefficient x conc. gradient

Flux through the air (gas) film: FA = kG(CA – CA,S)

Flux (mol/m2 h) = mass transfer coefficient x conc. gradient

Flux through the air (gas) film: FA = kG(CA – CA,S)

mass transfer coefficients

These equations are set up such that deposition flux

¾ The above equations are not useful in this form, because

Checking units: KOL is m/h, CA and CW are mol/m3 and

To repeat, this equation is set up such that deposition is positive

1. Bidleman, T., McConnell, L. Sci. Total Environ. 159: 101-117 (1995).

KOL is the overall mass transfer coefficient, which includes

1/KOL = 1/kL + RT/HkG

overall water film

1/KOL = 1/kL + RT/HkG

Situation #1: Air film resistance dominates

Ct and Co are solution

Using measured CW and CA, calculate (CW/CA)meas

D. Swackhamer et al., Environ. Sci. Technol. 33: 3864-3872 (1999)

Others use different relationships for kL and kG.