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![Page 1: How ocean CO 2 fluxes are estimated/measured Colm Sweeney [ csweeney@ldeo.columbia.edu ] Princeton University and Lamont-Doherty Earth Observatory.](https://reader036.fdocuments.net/reader036/viewer/2022062304/56649ecf5503460f94bdd98c/html5/thumbnails/1.jpg)
How ocean CO2 fluxes are
estimated/measured
Colm Sweeney[[email protected]]
Princeton Universityand
Lamont-Doherty Earth Observatory
![Page 2: How ocean CO 2 fluxes are estimated/measured Colm Sweeney [ csweeney@ldeo.columbia.edu ] Princeton University and Lamont-Doherty Earth Observatory.](https://reader036.fdocuments.net/reader036/viewer/2022062304/56649ecf5503460f94bdd98c/html5/thumbnails/2.jpg)
Outline
IV. Improving our estimates of air-sea fluxes- Time-space distribution of pCO2 - Parameterization of gas transfer velocity
III. Surface measurements:-Measurements of surface pCO2
-Methods for interpolation
II. The air-sea flux measurement-Covariance-Gradient technique
I. Concept-Ocean carbon chemistry primer-The air-sea flux
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Ocean Carbon Chemistry Primer
CO2(gas)
CO2 + H2O H2CO3
H3CO2 H+ + HCO3
-
HCO3- H+
+ CO32-
Carbonic acid
Bicarbonate
Carbonate
CO2 + CO32- 2 HCO3
-
TCO2
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Ocean Carbon Chemistry Primer
CO2(gas)
CO2 + H2O H2CO3
H3CO2 H+ + HCO3
-
HCO3- H+
+ CO32-
Carbonic acid
Bicarbonate
Carbonate
CO2 + CO32- 2 HCO3
-
280 atm 560 atm
8 mol kg-1
1617 mol kg-1
268 mol kg-1
15 mol kg-1
1850 mol kg-1
176 mol kg-1
1893 mol kg-1 2040 mol kg-1
100% pCO2 8% TCO2
TCO2
Taken from Feely et al. (2001)
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Concept
k =f(u*) Sc-n
u* – frictional velocity
s – solubilitySc – schmit number (v/D)n – 0.4 – 0.67 (high slope…low slope)
Net air-sea gas flux: Fgas=ks(pCO2w-pCO2a)
I=ks(pCO2a)River input:0.6 PgC yr-1
pCO2~2 atm
Keeling et al.
E=ks(pCO2w)
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Bomb 14C
Broecker and Peng (1994)
Transfer velocitykav = 22 cm/hru* = 7.4 m/s
Semi-infiniteHalf space
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Early estimates air-sea CO2 exchange
Natural14CO2/12CO2 in gassing
14CO2/12CO2 out gassing
n+14N14C
Decay: 14C 14N + e-
Pre-industrial assumption:14CO2 in = 14CO2 out + Decay
Solve for I
0.061 mol m-2 yr-1 uatm-1
=21.4 cm hr-1
seameansurfatm
VTCOCCC
][ 2
141414 CIA
CIA
C
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Early estimates air-sea CO2 exchange
Natural14CO2/12CO2 in gassing
14CO2/12CO2 out gassing
n+14N14C
Decay: 14C 14N + e-
Pre-industrial assumption:14CO2 in = 14CO2 out + Decay
Solve for I
0.061 mol m-2 yr-1 uatm-1
=21.4 cm hr-1
222Rn 218Po + 4He
[Rn]mixed layer Rn
[Rn]no loss Rn+ gas exchange
226Raaq 222Rngas + 4He
Outgassing of Radon
=
0.062 mol m-2 yr-1 uatm-1
=21.9 cm hr-1
[Rn]
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Flux Measurements in the Atmosphere
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Direct covariance technique
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Covariance flux of H2O and CO2
Fair-sea=<c'w'>
3-D SonicAnemometers
IR Detector(Sample)
H2O/CO2
samples
IR Detector(Motion Detection)
Std
Res
Pump
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Gradient Flux Technique
z
czwuFnet
)(c
2/1
Frictional velocity
MeasuredGradient (3-13m)
Gradient Function-empirically determinedbased on Monin Obukhov (MO)similarity theory
McGillis et al. (2001)
Covariance intake
z
c
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GasEx-98 Comparison-estimates of transfer velocity
GasEx-2001
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Estimates of gas transfer velocity
Rayleigh DistributionFor ocean wind speedsP(u)
k- short term
21)660/(
])([/
Scauk
uuPkan
nav
Bomb 14Ckav=22 cm /hr
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Estimates of CO2 fluxes from measurements of pCO2
1. Shipboard measurements of atmospheric and surface ocean pCO2
2. The ocean pCO2 climatology
3. Flux calculations using the climatology
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Shipboard measurements of atmospheric and surface ocean pCO2
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Equilibration of air sample
IR DetectorAir flow
Re-circulation
Drain
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Takahashi pCO2 database
1,183,000 measurements- Since ~1968
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Monthly distribution of pCO2
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The climatology1. Exclude all El-Nino years.
- dramatic change in annual fluxes have been observedEl-Nino periods based on SIO<-1.5 and SST changes.
2. Normalize pCO2 single reference year (1995)- In warm waters (lat. <45) pCO2 remains constant
3. Interpolate data on to 4ox 5ox 365 day grid-finite differencing algorithm is used with a 2-D transport model from Toggwieler et al. (1989) to propagate the influence of observed data at one day time steps. Distribution is solved iteratively
Time
pCO2
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The pCO2 Climatology
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Global CO2 flux
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Test of interpolation
pCO2
T0.28 C~0.8 PgC
=3.5%
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Sampling resolution 250K samples(Takahashi ’97)
500K samples(Takahashi ’99)
940K samples(Takahashi ’02)
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-3
-2
-1
0
1
2
N of 50N 14N-50N 14N-14S 14S-50S S of 50S Global
250K
500K
900KPgC
yr-1
Change in fluxes with increases in samples
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Gas Transfer Velocity and Fluxes
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Estimates using different gas exchange-wind speed relationships
Relationship Equation Flux
(Pg C yr-1)
Liss & Merlivat [1986] k= 0.17 U10 (U10
< 3.6 m s-1)
k= 2.85 U10 - 9.65 (3.6 m s-1<U10
< 13 m s-1)
k= 5.9 U10 - 49.3 (U10
> 13 m s-1)
-1.0
Wanninkhof [1992] [W-92] k= 0.39 U102 (long term averaged winds) -1.8
Wanninkhof&McGillis (1999)
[W&M-99]
k= 1.09 U10 - 0.333 U10
2 + 0.078 U103
(long term averaged winds)
-3.0
Nightingale et al. [2000] k= 0.333 U10 + 0.222 U10
2 -1.5
NCEP-41 year average windsb
[W-92]
k= 0.39 U102 (long term averaged winds) -2.2
Feely et al., 2001
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Long vs. short term winds
-4-3-2-1012
N of50N
14N -50N
14N-14S
14S-50S
S of50S
Global
W-92/41-yr
W-92/1995
W-99/41-yr
W-99/1995
PgC
yr-1
( uunn )
NCEP(1995) 41 Year average Monthly
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Sources of uncertainty
• Seasonal distribution of pCO2 (0.8 PgC)
• Estimate of skin temperature (-0.6 to –0.1 PgC)
• Estimates of the transfer velocity (20-40%)
• Estimates of windspeed (2 m/s)
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How can we do better?
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Factors influencing CO2 flux estimates
Wind
k pCO2
Air-Sea CO2Flux
SST
Transport
BiologyWindWaves
BubblesSurfaceFilm
Near SurfaceTurbulence
Bock et al. (1999)
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Better spatial-temporal coverage
2. Predictions using synoptic data sets:
1. Deployment of ships and moorings:
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time
space1 m2 1 km2 GlobeOcean
BasinRegional(106 km2)
centuries
decadal
Inter-annual
seasonal
daily
Remote sensing
Space and time coverage of ocean carbon observing networks
hourly
Process Studies
Repeat Trans-basin
Sections
VOS
surface pCO2
Shipboard
Time-Series
Moored
Time-Series
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Factors influencing surface water pCO2
dSdTALKdTCOdTd
S
pCO2
TALK
pCO22
TCO2
pCO2
T
pCO2pCO2
Temperature (C) -2 –30 (ln pCO2/T) = 0.0423oC-1 400%
Variable Range Relation Effect
TCO2(mol kg-1) 1900-2200 (ln pCO2/Tln TCO2) = 10 400%
Alkalinity(mol kg-1) 2150-2350 (ln pCO2/Tln TALK) = -9.4 -200%
Salinity(mol kg-1) 33.5-37 (ln pCO2/Tln S) = 0.94 ~10%
Alkalinity and salinity are proportional and can be accounted for
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Summer Fall
Winter Spring
Stephens et al., 1996
Temperature correlations
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Prediction of pCO2
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~
Bermuda
Courtesy of Nick Bates
~100 uatm
~9.5 C4.23% C-1
160 uatmDue to
temperature
dSdTALKdTCOdTd
S
pCO2
TALK
pCO22
TCO2
pCO2
T
pCO2pCO2
uatmdTCOTCO
pCO60~2
2
2
TCO2=33 mol/kg
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Temp vs. Biology
Takahashi et al. (2002)
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Tem
p. (
C)
CO2+H2O O2+CH2O Upwelling
PalmerSta.
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MODIS
May 2001
Sea Surface Temperature
May 2001
Chlorophyll
PAR December 2000
Derived from GSFC Data Assimilation Office 3 hr retrievals.
http://modis-ocean.gsfc.nasa.govhttp://opp.gsfc.nasa.gov
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Predicting pCO2
NPP
SST
Zmix
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Estimates of gas transfer velocityWind
k
WindWaves
BubblesSurfaceFilm
Near SurfaceTurbulence
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0
20
40
60
80
0 50 100 150
k(600)
[cm
·h-1]
Rn [mm·h-1]
k(600)0.929 0.679Rn 0.0015Rn2
Gas exchange vs. rain rate (MP distribution)
Ho et al. 1997
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Summary
III. Improving our estimates of air-sea fluxes- Time-space distribution of pCO2
- Deployment of ships and buoys- Use of satellite measurements to calculate change in TCO2
- Parameterization of gas transfer velocity- micro-scale measurements
II. Estimates using surface pCO2:- Provide us with estimates of fluxes on a monthly basis based climatology adjusted for a single non-El Nino year- Errors in flux estimates occur due to lack of direct pCO2, wind speed and understanding of the gas transfer velocity
I. The air-sea flux measurement- Provide true short-term (~1 hr) measurements of flux which can be associated with wind speeds measured on that same time scale. - Are limited to areas of high pCO2
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Inventory methods
• Estimates of integrated change in carbon inventory1) Time series approach
– Comparing measurements made between two time intervals
– Compare residuals of multiple parameter regressions using T, S, TALK and nutrients
2) C* Method– Estimate of the total inventory of anthropogenic carbon
in any given region
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Hydrographic samplisg stations
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C* Method (Gruber et al.)
C*
170O2
116CO2
Soft tissue
[O2]sat-O2 [O2]meas =0
T170 O216 NO32-
Carbonate
pCO2(i)=280
CaCO3
Ca2++CO32-
Cant = Cm – ∆Cbio – Ceq280 – Cdiseq = ∆C* - ∆Cdiseq
∆Cbio=rC:OO2+ ½(rN:OO2+CO32-)
Cdiseq
Ceq280
∆Cbio
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Anthropogenic CO2
(mol kg-1)
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(m
ol k
g-1)
Pre-industrial CO2
![Page 52: How ocean CO 2 fluxes are estimated/measured Colm Sweeney [ csweeney@ldeo.columbia.edu ] Princeton University and Lamont-Doherty Earth Observatory.](https://reader036.fdocuments.net/reader036/viewer/2022062304/56649ecf5503460f94bdd98c/html5/thumbnails/52.jpg)
International CLIVAR/CO2 Lines (including US)
CO2 Clivar Repeat Hydro.