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http://press.princeton.edu/titles/8223.html
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http://www.up.ethz.ch/people/ngruber/publications
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DefinitionDefinition: discipline studying the chemical reactions and
processes within the ocean and those between the ocean and its borders
Chemical oceanographyChemical oceanography mainly mainly studies the cycles of the elements studies the cycles of the elements forming seawater, these are the forming seawater, these are the biogeochemical cyclesbiogeochemical cycles. .
=> Movement of the elements and => Movement of the elements and compounds within the organisms compounds within the organisms and the environmentand the environment
Gruber 2004
ESQUEMA CICLO DEL C, N, O2, P EN EL OCÉANO
Physical oceanography
Biological oceanography
Geological oceanography
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Global carbon cycle
+65 -125
1.7 Land use change
+18
21.9 20
1.9 Land sink
1.6
+100
5.4
-220
+161
& the anthropogenic perturbation
PgC/yr = 10 15 gC = 1 000 000 000 tons = 1 billón de kilos
1 tonelada = 1 000 000 gC = 1000 kilos
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RelevanceRelevance:
• inmense carbon reservoir, 50 times the carbon in the atmosphere, specially inorganic carbon
• air-sea exchange of CO2 is relatively quick
• the oceans absorb between 26 and 44% of the anthropogenic CO2 driven into the atmosphere
• the CO2 uptaken by the ocean: => it does not affect the earth radiactive balance => mitigates the greenhouse effect
=> sequestered on long time scales, much longer than in the terrestial biosphere
Carbon accumulation on real scalesCarbon accumulation on real scales
Antia, NATO Summer School, Ankara, 2006
On a time scale of millenia: On a time scale of millenia:
the oceans determine the CO2 concentration in the atmospherethe oceans determine the CO2 concentration in the atmosphere
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Fluxes in PgC/yr & stocks in PgC
DIC: dissolved inorganic carbon; DOC: dissolved organic carbon
POC: particulate organic carbon; PIC: particulate inorganic carbon = CaCO3
NPP: net primary production
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Chisholm, Nature 2000
Biological pumpBiological pump Physical or Physical or solubility pumpsolubility pump
Primary Prod.Primary Prod.100100
Export > 100mExport > 100m1010
SedimentsSediments0.10.1
Temporal Temporal Scale Scale 1 year1 year
100-1000 years100-1000 years
> 10> 1066 years years
weeks weeks
Photic layer, Photic layer, epi-pelagicepi-pelagic
Who plays Who plays here?here?
Aphotic layer: meso Aphotic layer: meso & bati-pelagic& bati-pelagic
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Biological processesBiological processes::
+ soft-tissue pump: photosynthesis/ remineralization of OM + soft-tissue pump: photosynthesis/ remineralization of OM
+ carbonate pump: formation/dissolution of CaCO+ carbonate pump: formation/dissolution of CaCO33
1 mol CaCO3=> 0.6 mol CO2
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Organic matter synthesis – stoichiometry - Redfield ratiosOrganic matter synthesis – stoichiometry - Redfield ratios::
Redfield ratiosRedfield ratios::
+ C:N:P:O+ C:N:P:O22
+ 106:16:1:-138+ 106:16:1:-138
+ mean phyto composition (lipids + + mean phyto composition (lipids + proteins + sugars + nucleid acids) in the proteins + sugars + nucleid acids) in the ocean … BUT … it varies … ocean … BUT … it varies …
+ what else??+ what else??
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Organic matter synthesisOrganic matter synthesis- limiting factors - nutrients- limiting factors - nutrients
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Where do they come from?Where do they come from?
+ atmosphere+ atmosphere
+ lateral transport+ lateral transport
+ vertical transport: upwelling, + vertical transport: upwelling,
winter mixing, vertical mixingwinter mixing, vertical mixing
Chisholm, Nature 2000
Organic matter synthesisOrganic matter synthesis- limiting factors - nutrients- limiting factors - nutrients
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¿ De dónde vienen?¿ De dónde vienen?
+ atmósfera+ atmósfera
+ transporte lateral+ transporte lateral
+ transporte vertical: upwelling, winter mixing, vertical + transporte vertical: upwelling, winter mixing, vertical mixingmixing
Organic matter synthesisOrganic matter synthesis- limiting factors - nutrients- limiting factors - nutrients
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Organic matter synthesis Organic matter synthesis – limiting factors – nutrients – limiting factors – nutrients
- light + ????- light + ????
Euphotic zone:Euphotic zone: area well iluminated, where area well iluminated, where photosynthesis takes place, but it depends on photosynthesis takes place, but it depends on turbidity, hours of light, balance between turbidity, hours of light, balance between photosynthesis and respirationphotosynthesis and respiration
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Definitions
P= phytoplancton
Z= zooplancton
B= bacteria
DON: dissolved organic nitrogen
PON: particulate organic nitrogen
More concepts: More concepts: new, regenerated and export productionA
tmosp
heri
c in
put
Vert
ical input
Exp
ort
as
part
icu
late
Exp
ort
or
import
as
dis
solv
ed
Production & recycling
Mainly production
N fixation
f ratio = f ratio = New Prod / Primary productionNew Prod / Primary production
e ratio = e ratio = export prod / PPexport prod / PP
over long time and space scales f ratio = e ratioover long time and space scales f ratio = e ratio
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Biological efficiency: Biological efficiency: capacity to consume the nutrients available in the photic zone
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ICE: ICE: the marginal sea iceSPSP: subpolarST-SS/PSST-SS/PS: Subtropical Seasonally / Permanently Stratified EQ-D/EQ-UEQ-D/EQ-U: Equatorial downwelling/upwellingLL-U:LL-U: low-latitude upwelling biome
OCEAN BIOMASOCEAN BIOMAS
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The efficiency of the biological pump is The efficiency of the biological pump is inversely correlated to the efficiency in inversely correlated to the efficiency in the export of organic matter out of the the export of organic matter out of the photic zonephotic zone
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The input of nutrients, light, physical conditions, etc.. Affect the efficiency of The input of nutrients, light, physical conditions, etc.. Affect the efficiency of the biological pump, but the export mainly depends on the community the biological pump, but the export mainly depends on the community structure, which organisms are in the photic zone. structure, which organisms are in the photic zone.
Export depends on temperature + nutrients input + FeExport depends on temperature + nutrients input + Fe
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1 mol CaCO3=> 0.6 mol CO2
Rain Ratio = POC / PIC exportRain Ratio = POC / PIC export
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La eficiencia del secuestro depende del transporte de carbono por La eficiencia del secuestro depende del transporte de carbono por debajo de la capa de mezcla invernal (WML)debajo de la capa de mezcla invernal (WML)
Secuestro de C = Flujo POC · [(Rain Ratio-0.6)/ Rain Ratio]Secuestro de C = Flujo POC · [(Rain Ratio-0.6)/ Rain Ratio]
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Producción primariaProducción primaria
Secuestro de C bajo WMLSecuestro de C bajo WML
Moderada PP- Bajo secuestro – WML profundo
Alta PP- Alto secuestro – WML somero
Antia et al. (GBC, 2001)
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PgC/yr = 10 15 gC = 1 000 000 000 toneladas = 1 billón de kilos
1 tonelada = 1 000 000 gC = 1000 kilos
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pH
TIC
Complex systemComplex system:
• Equilibrium system controlled by T, S & pressure
• thanks to it, seawater is a weak alcaline buffer, pH varies within a 7.5 and 8.5
• 4 variables: TIC, pH, TA, fCO2
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fCO2 = x(CO2) patm = [CO2]/0(S,T)
AT=[HCO3-]+2·[CO3
2-]+[B(OH)4-]+[OH-]-[H3O+]
CT=[CO2] + [HCO3-] + [CO3
2-]
Mass balanceMass balance
Charge balanceCharge balance
pH= -log [H3O+]
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fCO2 = x(CO2) patm = [CO2]/0(S,T)
General rule:
more dissolved CO2 in cold waters
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CT=[CO2] + [HCO3-] + [CO3
2-]
Mass balanceMass balance
(CT a.k.a. CO2 or DIC or TIC)
Independent of T & Pr
pH
TIC
1%
85%
14%
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Explicit approach: Explicit approach:
5 species (unknowns) 5 species (unknowns) H H22COCO
33* , HCO* , HCO33
–– , CO , CO33
–2 –2 , H , H++ , OH , OH––
3 equilibrium equations3 equilibrium equations K K11, K, K
22, Kw , Kw
1 concentration condition1 concentration condition C CTT
1 proton condition1 proton condition Alk Alk
Any Any twotwo carbonate system parameters fix the values of all the rest: carbonate system parameters fix the values of all the rest: CCTT , , AlkAlk , H , H
22COCO33* (or * (or pCOpCO
22), HCO), HCO33
–– , CO , CO33
–2 –2 , , pHpH
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+ Table 2 Millero et al. (1993) showing estimates of the analytical precision (reproducibility) and accuracy of measurements of pH, TA, TIC and fCO2:
Analysis Precision Accuracy Reference pH (spectrofot.) ±0.0004 ±0.002 Clayton & Byrne (1993)TA (potentiom.) ±2 umol/kg ±4 umol/kg Millero et al. (1993)TIC (coulometric) ±1 umol/kg ±2 umol/kg Johnson et al. (1993)fCO2 (infrared) ±0.5 uatm ±2 uatm Wannikhof & Thoning (1993)
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+ Table 3 Millero et al. (1993) with the estimated errors in the calculated parameters of the CO2 system using various input measurements
Input pH TA TIC fCO2
Accuracy ±0.002 ±2 umol/kg ±2 umol/kg ±2 uatm.
pH-TA ±3.8 ±2.1 pH-TIC ±2.7 ±1.8 pH-fCO2 ±21 ±18 fCO2-TIC ±0.0025 ±3.4 fCO2-TA ±0.0026 ±3.2 TA-TIC ±0.0062 ±5.7
Total error: squared root of the errors due to each input parameter
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pH
in
cre
as
e
pH increase
Zeebe and Wolf-Galdrow (2001)
Three pumps:Three pumps:
- gas-exchange: T + bio
- Soft tissue
- Carbonate
Chisholm, Nature 2000
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Factores físicosFactores físicos::
+ intercambio aire-agua+ intercambio aire-agua
+ disolución en el agua+ disolución en el agua
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Physical factorsPhysical factors::
+ air-sea exchange+ air-sea exchange
Piston velocity, units of velocity
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¿CO2 equilibration time in the mixed layer?¿CO2 equilibration time in the mixed layer?
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Takahashi et a. (DSRII, 2002)
Questions:
+ why are there sinks and sources of CO2 ?
+ what factors control pCO2?
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Physical factorsPhysical factors::
+ temperature+ temperature
+ salinity+ salinity
122
2·0423.0
ln·
1 CT
pCO
T
pCO
pCO
1ln
ln· 22
2
S
pCO
S
pCO
pCO
S
pCO2 = 300 uatm, T= 20, S=35pCO2 = 300 uatm, T= 20, S=35
- 1ºC increase in T => +13 uatm1ºC increase in T => +13 uatm
- 1 unit increase in S => + 9 uatm1 unit increase in S => + 9 uatm
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biotemp pCOpCOpCO 222
Quantification of the biological and physical factors:Quantification of the biological and physical factors:
MinTobsMaxTobstemp pCOpCOpCO 222
)(*0423.0exp(*22 meanobsTmeanTobs TTpCOpCO
Seasonal variations in Temp Seasonal variations in Temp are high in subtropical areas, are high in subtropical areas, tropical and polar areas have tropical and polar areas have limited variability in T and limited variability in T and so on pCOso on pCO22
temptemp
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tempbio pCOpCOpCO 222
pCO2 decreases due to pCO2 decreases due to biological activity biological activity (photosynthesis) north of (photosynthesis) north of 40ºN, subpolar areas, 40ºN, subpolar areas, upwelling areas.upwelling areas.
Quantification of the biological and physical factors:Quantification of the biological and physical factors:
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BiologyBiology: green-blue, : green-blue, high north latitudes, high north latitudes, Eq. Pacific, SOEq. Pacific, SO
TempTemp: temperate & : temperate & subtropical areassubtropical areas
!!!!: areas of water : areas of water mass formation, mass formation, biology biology predominates.predominates.
Quantification of the biological and physical factors:Quantification of the biological and physical factors:
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The Royal Society (2005)
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-60 -40 -20 0 20 40 60
Latitude (º)
-6000
-5000
-4000
-3000
-2000
Dep
th (
m)
7.50
7.55
7.60
7.65
7.70
7.75
7.80
7.85
7.90
7.95
8.00
8.050
-1000
-500
-1500
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Caldeira & Wickett (2003)
Oceanography (Vol 17, 2004)
Oceanography (Vol 17, 2004)
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-60 -40 -20 0 20 40 60
Latitude (º)
-6000
-5000
-4000
-3000
-2000
Dep
th (
m)
33.8
34
34.3
34.5
34.8
35
35.2
35.5
35.7
36
36.2
36.4
36.7
36.90
-1000
-500
-1500
Salin ity
-60 -40 -20 0 20 40 60
Latitude (º)
-6000
-5000
-4000
-3000
-2000
Dep
th (
m)
-2 ºC
0 ºC
2 ºC
4 ºC
6 ºC
8 ºC
10 ºC
12 ºC
14 ºC
16 ºC
18 ºC0
-1000
-500
-1500
T heta
-60 -40 -20 0 20 40 60
Latitude (º)
-6000
-5000
-4000
-3000
-2000
Dep
th (
m)
2060
2080
2100
2120
2140
2160
2180
2200
2220
2240
22600
-1000
-500
-1500
T otal Inorgan ic C arb on
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Global mean profiles of the three main carbon pumps.
Sarmiento & Gruber (2006)Sarmiento & Gruber (2006)
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-60 -40 -20 0 20 40 60
Latitude (º)
-6000
-5000
-4000
-3000
-2000
Dep
th (
m)
33.8
34
34.3
34.5
34.8
35
35.2
35.5
35.7
36
36.2
36.4
36.7
36.90
-1000
-500
-1500
Salin ity
-60 -40 -20 0 20 40 60
Latitude (º)
-6000
-5000
-4000
-3000
-2000
Dep
th (
m)
2280
2295
2310
2325
2340
2355
2370
2385
2400
24150
-1000
-500
-1500
T otal A lk alin ity
-60 -40 -20 0 20 40 60
Latitude (º)
-6000
-5000
-4000
-3000
-2000
Dep
th (
m)
2290
2305
2320
2335
2350
2365
2380
23950
-1000
-500
-1500
NTA = TA*35 / SalNTA = TA*35 / Sal
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Relevance of the coastRelevance of the coast
LOICZ, 2006
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Relevancia costas:Relevancia costas:
ocupan ocupan ±± 20% de la superficie del océano 20% de la superficie del océano
contienen más de un 40% de la población mundialcontienen más de un 40% de la población mundial
proveen de 75% de las capturas de pescaproveen de 75% de las capturas de pesca
representan un 25% de la PP representan un 25% de la PP
directamente afectadas por la actividad humana directamente afectadas por la actividad humana (contaminación, eutrofización): ríos, aerosoles en atmósfera, (contaminación, eutrofización): ríos, aerosoles en atmósfera,
interacción tierra-océano-atmósfera-sedimentos en escalas de interacción tierra-océano-atmósfera-sedimentos en escalas de años.años.
muy heterogéneas y dinámicas, vehículo conductor de carbono muy heterogéneas y dinámicas, vehículo conductor de carbono hacia el interior del océano.hacia el interior del océano.
proyectos: LOICZ (1992-2005-2012), CARBOOCEAN (2005-proyectos: LOICZ (1992-2005-2012), CARBOOCEAN (2005-2009)2009)
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0.24 PIC0.32 POC
33.6 DIC, 1.44 DOC,0.012 PIC, 0.26 POC
33.92 DIC, 0.84 DOC0.048 POC
CARBON budget (PgC yCARBON budget (PgC y-1-1) in the continental margins) in the continental margins
0.18 PIC0.18 POC
River, drainage & ice
Primary Prod: 0.48 PIC, 6.19 POCNew Prod.:0.28 DOC, 0.23 PIC, 0.50 POC
Coast & open platforms0.38 DIC, 0.32 DOC,0.18 PIC, 0.22 POC
0.0012 CH4 from sediments0.0017 DMS from biolog. Act.
Sediments & fishery
Open ocean
Mixed layer
Deep layer
Sediments
0.0036 CPrecipitation & dust
Atmosphere
Chen (2004)Chen (2004)Chen & Borges (2009)Chen & Borges (2009)
0.31 IC (DIC)0.31 IC (DIC)0.81 OC (74% DOC)0.81 OC (74% DOC)
Net sink ofNet sink of COCO22
CONTINENTAL SHELF PUMPCONTINENTAL SHELF PUMP
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Wollast (1998)Wollast (1998)
0.36 CO0.36 CO22
New Prod 0.25 PIC
0.0008 DMS
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Net air-sea CONet air-sea CO22 flux on european coasts flux on european coasts
Borges et al., ECSS, 2006Frankingnoulle & Borges GBC 2001
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Borges et al., ECSS, 2006
Golfo de Vizcaya-0.8 molC m-2 yr-1
Net air-sea CONet air-sea CO22 flux on european coasts flux on european coasts
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