Lecture 7 Gases and Gas Exchange

Composition of the atmosphere Gas Exchange Fluxes

Gas solubility Effect of wind
Global CO2 fluxes by gas exchange

Emerson and Hedges: Chpts 3 and 10

 Sarmiento and Gruber (2002) Sinks for Anthropogenic Carbon
Physics Today August 2002 30-36

Q. Was pre-industrial (PI) CO2 at steady state?

Q. Is atm CO2 at steady state today?
Composition of the Atmosphere
More than 95% of all gases except radon reside in the atmosphere.
The atmosphere controls the oceans gas contents for all gases except radon, CO 2 and H2O.

Gas Mole Fraction in Dry Air (fG) molar volume at STP (l mol-1 )
where fG = moles gas i/total moles 22.414 for an ideal gas (0°C)

N2 0.78080 22.391
O2 0.20952 22.385
Ar 9.34 x 10-3 22.386
CO2 3.9 x 10-4 22.296
Ne 1.82 x 10-5 22.421
He 5.24 x 10-6 22.436

H2 O ~0.013

Q. Why is dry air used?

Some comments about units of gases:

In Air In Water
Pressure - Atmospheres Volume - liters gas at STP / kgsw
1 Atm = 760 mm Hg STP = standard temperature and pressure
Partial Pressure of Gasi = P (i) /760 = 1 atm and 0C (= 273ºK)

Volume - liters gas / liters air Moles - moles gas / kgsw

(ppmv = ml / l, etc)
- moles gas I / total moles
Conversion: lgas/kgsw / lgas / mole = moles/kgsw
(~22.4 l/mol)
Dalton's Law
Gas concentrations are expressed in terms of pressures.
Total Pressure = SPi = Dalton's Law of Partial Pressures
PT = PN2 + PO2 + PH2O + PAr + .........

Dalton's Law implies ideal behavior -- i.e. all gases behave independently
of one another (same idea as ideal liquid solutions with no electrostatic interactions).
Gases are dilute enough that this is a good assumption.

Variations in partial pressure (Pi) result from:

1) variations in PT (atmospheric pressure highs and lows) range = 32 to 25 inch Hg
2) variations in water vapor ( PH2O)

We can express the partial pressure (Pi) of a specific gas on a dry air basis as follows:
Pi = [ PT - h/100 Po ] fg
where Pi = partial pressure of gas i
PT = Total atmospheric pressure
h = % relative humidity
Po = vapor pressure of water at ambient T
fg = mole fraction of gas in dry air (see table above)
Humidity Example:
Say we have a humidity of 80% today and the temperature is 15C

Vapor pressure of H2O at 15C = Po = 12.75 mm Hg (from reference books)

Then, PH2O = 0.80 x 12.75 = 10.2 mm Hg

If PT = 758.0 mm Hg

PT,Dry = (758.0 - 10.2) mm Hg

= 747.8 mm Hg

Then: fH2O = PH2O / PT = 10.2 / 758.0 = 0.013

So for these conditions H2O is 1.3% of the total gas in the atmosphere.
That means that water has a higher concentration than Argon (Ar).

This is important because water is the most important greenhouse gas!

Example: Units for CO2

Atmospheric CO2 has increased from 280 (pre-industrial) to 398 (present) ppm.

In the table of atmospheric concentrations (see slide 3)

fG,CO2 = 3.9 x 10-4 moles CO2/total moles
= 390 x 10-6 moles CO2/total moles
= 390 ppm

This can also be expressed in log form as:

= 100.59 x 10-4 = 10-3.41

Example: Units for Oxygen

Conversion from volume to moles

Use O2 = 22.385 L / mol at standard temperature and pressure (STP)

if O2 = 5.0 ml O2/LSW

then

5.0 ml O2 / Lsw x mol O2 / 22,385 ml = 0.000223 mol O2 / Lsw

= 223 mol O2 / Lsw

Solubility
The exchange or chemical equilibrium of a gas between gaseous and liquid phases
can be written as:
A (g)  A (aq)

At equilibrium, we can define the ration using an equilibrium constant:

K = [A(aq)] / [A(g)]

There are two main ways to express solubility (Henry’s Law and Bunsen Coefficients).
1. Gas Solubility - Henry's Law:
We can express the gas concentration in terms of partial pressure using the
ideal gas law:
PV = nRT P = pressure, V = volume, n = # moles
R = gas constant = 8.314 J K-1 mol-1, T = temp K

so that the number of moles n divided by the volume is equal to [A(g)]

n/V = [A(g)] = PA / RT where PA is the partial pressure of A

Then K = [A(aq)] / PA/RT

or [A(aq)] = (K/RT) PA

[A(aq)] = KH PA units for K are mol kg-1 atm-1;

in mol kg-1 for PA are atm

Henry's Law states that the concentration of a gas in water is proportional

to its overlying partial pressure.

KH is mainly a function of temperature with a small impact by salinity.

 Example (Solubility at 0C):
Partial Pressure = Pi = fG x 1atm total pressure

Gas Pi KH (0C , S = 35) Ci (0C, S = 35; P = 760 mm Hg)

N2 0.7808 0.80 x 10-3 624 x 10-6 mol kg-1

O2 0.2095 1.69 x 10-3 354 x 10-6
Ar 0.0093 1.83 x 10-3 17 x 10-6
CO2 0.00033 63 x 10-3 21 x 10-6

Example
The value of KH for CO2 at 25C is 29 x 10-3 moles kg-1 atm-1 or 2.9 x 10-2 or 10-1.53.
The partial pressure of CO2 in the atmosphere is increasing every day
but if we assume that at some time in the recent past it was 350 ppm
that is equal to 10-3.456 atm.

See Emerson and Hedges: Table 3.6 for 20°C and Table 3A1.1 for regressions for all T and S
Example: What is the concentration of CO2 (aq) in equilibrium with the atmosphere?

For PCO2 = 350 ppm = 10-3.456 and T = 25°C

For CO2 KH = 29 x 10-3 = 2.9 x 10-2 = 10-1.53 moles /kg atm

then

CO2 (aq) = KH x PCO2 = 10-1.53 x 10-3.456 = 10-4.986 mol kg-1

= 10+0.014 10-5 = 1.03 x 10-5 = 10.3 x 10-6 mol/l at 25C (0.5% of DIC)

The equilibrium concentration of CO2(aq) will be dependent only on PCO2 and temperature.

CO2(aq) is independent of pH.

But this is only the first step!

Controls on Solubility

Summary of trends in solubility:

1. Type of gas:
KH goes up as molecular weight
goes up (note that CO2 is anomalous)
See solubility table.
2. Temperature:
Solubility goes up as T goes down
Major effect

3. Salinity:
Solubility goes up as S goes down
Minor effect
Temperature control
on gas concentrations

O2 versus temperature
in surface ocean

solid line equals saturation

for S = 35 at different
temperatures

average supersaturation
≈ 7 mmol/kg (~3%)
Causes of deviations from Equilibrium:
Causes of deviation from saturation can be caused by:

1. nonconservative behavior (e.g. photosynthesis (+) or respiration (-)

or denitrification (+))
2. bubble or air injection (+)
3. subsurface mixing - possible supersaturation due to non linearity of
KH or a vs. T.
4. change in atmospheric pressure - if this happens quickly, surface
waters cannot respond quickly enough to reequilibrate.
Rates of Gas Exchange
Stagnant Boundary Layer Model.
well mixed atmosphere

Cg = KH Pgas = surface SW in
ATM equil. with atm
0
OCN Stagnant Boundary
Layer –
ZFilm transport by
Depth (Z) molecular diffusion
CSW

well mixed surface SW

Z is positive downward
C/ Z = ­
F = + (flux into ocean)
Flux of Gas
The rate of transfer across this stagnant film
occurs by molecular diffusion from the region
of high concentration to the region of low concentration.
Transport is described by Fick's First Law ( with fixed boundary conditions)
which states simply that flux is proportional to
the concentration gradient..

F = - D d[Cg] / dZ
where
D = molecular diffusion coefficient in water (= f (gas and T)) (cm 2sec-1)
dZ is the thickness of the stagnant film on the ocean side (Z film)(cm)
d[Cg] is the concentration difference across the stagnant film (mol cm -3)

The water at the top of the stagnant film (Cg) is assumed to be

in equilibrium with the atmosphere. We can calculate this value
using the Henry's Law equation for gas solubility.

The bottom of the film has the same concentration as the mixed-layer (C SW).

Thus: Flux = F = - D/Zfilm (Cg - CSW) = - D/Zfilm (KHPg - CSW)

Because D/Zfilm has velocity units, it has been called the Piston Velocity (k)

e.g., D = cm2 sec-1

Z film = cm

Typical values are D = 1 x 10-5 cm2 sec-1 at 15ºC

Zfilm = 10 to 60 mm (from 222Rn and 14C)

Example:
D = 1 x 10-5 cm2 sec-1
Zfilm = 17 mm determined for the average global ocean using 14C data
Thus Zfilm = 1.7 x 10-3 cm

The piston velocity = D/Z = k = 1 x 10-5 cm2 s-1 /1.7 x 10-3 cm

= 0.59 x 10-2 cm/sec
5m/d note: 1 day = 8.64 x 104 sec

Each day a 5 m thick layer of water will exchange its gas with the atmosphere.

For a 100m thick mixed layer the exchange will be completed every 20 days.
 Gas Exchange and Environmental Forcing: Wind
Wanninkhof, 1992
from 14C
100
Tra c e r N-2 0 0 0
Tra c e r Wa t -9 1
Tra c e r-Wa n n
Rn
80
C-1 4 b om b
C-1 4 na t
k, 6 0 0 W-9 2
k, 6 0 0 L&M
k, 6 0 0 ( cm / hr)

60 S-8 6
W-9 9

40

~ 5 m d-1 20 Liss and Merlivat,1986

from wind tunnel exp.

0
0 5 10 15 20

U ( m/ s)
20 cm hr-1 = 20 x 24 / 102 = 4.8 m d-1 10
One of main goals of JGOFS was
to calculate the CO2 flux across
the air-sea interface

Flux = F = - D/Zfilm (Catm - CSW) = - D/Zfilm (KHPatm - CSW)

= - D/Zfilm (KHPatm – KHPSW)

= -D/Zfilm KH (Patm – PSW)

See Boutin Figure
 Expression of Air -Sea CO2 Flux
Magnitude
Mechanism
Apply over larger space time domain
k-transfer velocity S – Solubility
From Sc # & wind speed From SST & Salinity

F = k s (pCO2w- pCO2a) = K ∆ pCO2

pCO2a
pCO2w
From measurements From CMDL
and proxies CCGG network
Global Map of Piston Velocity (k in m yr-1) times CO2 solubility (mol m-3) = K
from satellite observations (Nightingale and Liss, 2004 from Boutin).

At high latitudes T - so Solubility  and wind -so k Thus k x S

 ∆pCO2 fields

Overall trends known:

* Outgassing at low latitudes (e.g. equatorial)

* Influx at high latitudes (e.g. circumpolar)

* Spring blooms draw down pCO2 (N. Atl)

* El Niños decrease efflux

JGOFS Gas Exchange Highlight #4 -
∆pCO2 fields:Takahashi climatology

Monthly changes in pCO2w

 Fluxes: JGOFS- Global monthly fluxes

Combining pCO2 fields with k: F = k s (pCO2w- pCO2a)

 On first order flux and ∆pCO2 maps do not look that different
http://www.ldeo.columbia.edu/res/pi/CO2/carbondioxide/pages/pco2_flux_rate_maps.html
 CO2 Fluxes: Status

Do different parameterizations between gas exchange and wind matter?

Global uptakes
Liss and Merlivat-83: 1 Pg C yr-1
Wanninkhof-92: 1.85 Pg C yr-1
Wanninkhof&McGillis-98: 2.33 Pg C yr-1
Zemmelink-03: 2.45 Pg C yr-1

Yes!

Global average k (=21.4 cm/hr): 2.3 Pg C yr-1

We might not know exact parameterization with forcing but forcing is

clearly important
Compare with net flux of 2.1 PgCy-1 from Quay et al (1992)
and 2.2 PgCy-1 from Mikaloff Fletcher et al (2006)
 Solubilities of Gases in Seawater
from Broecker and Peng, (1982)
Bunson
Coefficient Henry’s Law

Solubility increases with Concentration ratio for

KH = 29 x 10-3
mole weight and equal volumes of air and
decreasing temperature = 2.9 x 10-2
water.
= 10-1.53
Gas Solubility - CFCs
 Effect of El Nino on ∆pCO2 fields
High resolution pCO2 measurements in the Pacific since Eq. Pac-92

Eq Pac-92 process study

PCO2sw

Always greater
than atmospheric Cosca et al. in press
-2

-1

ENSO INDEX (MEI)

El Nino Index 1

4
1985 1990 1995 2000

year