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Jacek Piskozub Institute of Oceanology PAS Sopot, Poland

Lecture 3: Ocean as the sink and source of climatically important gases (carbon cycle, CO2, methane, DMS)‫‏‬

Ho Chi Minh City, December 2007

Jacek Piskozub
Hi Chi Minh City lectures, December 2007

Ecosystem approach to valuation of marine coasts: examples from Baltic Sea Marine aerosol source function: approaching the consensus Ocean as the sink and source of climatically important gases Air sea interaction in the global scale: from multidecadal variability to Arctic Oscillation Climate change threats, Part I: Changes in the climate of the tropic Climate change threats, Part II: Arctic climate and global sea level

How do the greenhouse gases work?

A simple application of fundamental laws of physics and geometry results in an Earth which is on average 33 K cooler if there were no “greenhouse gases”, namely H2O, CO2, CH4.

Efekt cieplarniany

Proste użycie podstawowych praw fizyki i geometrii pozwala wyliczyć, że Ziemia byłaby 33 stopnie zimniejsza gdyby nie „gazy cieplarniane” H2O, CO2, CH4.

Greenhouse effect: co absorption in infrared

Greenhouse gases absorb infrared (IR) radiation making it more difficult for Earth to cool down by radiating heat into the outer space. Because different gases have different absorption bands, together they are able to absorb in almost all the IR wavelength range. The visible (VIS) range is actually one of the few windows of transparency for electromagnetic waves.

IPCC report: what we knew in 2007

IPCC, Climate Change 2007: The Physial Science Basis

Atmospheric O2 & CO2 history: a wider view
Method: Our best guess of atmospheric O2 (upper panel) and CO2 (lower panel) concentration from sedimentary C13, and long-term carbon cycle modelling (volcanism, subduction metabolism, erosion etc.) Conclusion: CO2 concentration decreases gradually in the geological time scale – but with a lot of oscillations. Atmospheric O2 & CO2 concentration in the Phanerozoic (N.

Lane “Oxygen” 2005 after Berner & Canfield 1989, Berner 1994)

Atmospheric CO2 increase since 1958

Atmospheric CO2 concentration measured on Mauna Loa (Hawaii) 1958-2005 (Keeling & Whorf,

Charles D. Keeling 1928-2005

Latest five years of the CO2 trend

The increasing trend in atmospheric CO2 does not change. Since the Mauna Loa measurements were started in 1958, every year brings more atmospheric carbon dioxide.


How much of the carbon stays in atmosphere?
1Pg = 1 Gt = 1 Tkg = 1012 kg

We produce yearly 6 PgC (recently even more!) by burning fossil fuels (coal, oil and natural gas) and possibly 2 PgC more by clearing forests. Roughly one half stays in the atmosphere. What happens with the rest?

Houghton 2007 (Annu. Rev. Earth Planet.)‫‏‬

How to check how much of a CO2 sinks in the ocean?

Changes in the atmospheric O2/N2 ratio make it possible to differentiate land and sea of CO2. It is assumed that the land biosphere gives back 1.1 mole of O2 for each absorbed CO2 mole, while the ocean does not return any oxygen.
Keeling, Piper & Heimann 1996 (Nature.)‫‏‬

What happens to the fossil fuel carbon?

Only part of the CO2 we produce stays in the atmosphere. The rest is absorbed by the ocean or land vegetation (here named: “Unidentified sink”).
Houghton 2007 (Annu. Rev. Earth Planet.)‫‏‬

Quay 2002 (Science)‫‏‬

How much goes into the ocean?

Ocean absorbs about 25% of the CO 2 we produce. The terrestrial (land) vegetation absorbs on aveage a similar amount (the maximum around 1990 may be connected to Pinatubo volcano). Houghton 2007 (Annu. Rev. Earth Planet.)‫‏‬

Ile do oceanu a ile pochłania życie na lądzie?

Left: variability of CO2 flux on land (A) is greater than for the ocean (B). Right: carbon balance for the tropical Pacific (A) and tropical land (B). Arrows are the El Niño events (bold ones mean strong events).
Bousquet et al. 2000 (Science)‫‏‬

Where on land?

Anomalies of CO2 fluxes from horizontal concentration gradients for Northern Hemisphere, North America. and Eurasia (vertical axis: down for sink, up for source).
Bousquet et al. 2000 (Science)‫‏‬

Carbon cycle

Deep ocean is the main reservoir of organic carbon (if one does not count the sediments in Earth crust). Therefore the ocean controls atmospheric CO 2 concentrations in the time scale of hundreds and thousands of years (for longer time scales the controlling factor is geology).

Sigman & Boyle 2000 (Nature)‫‏‬

Carbon cycle: reservoirs and fluxes in Pg.

Houghton 2007 (Annu. Rev. Earth Planet.)‫‏‬

What does the future bring?

Land biosphere accepts less CO 2 with increasing temperature (“soil respiration”) therefore during El Niños, atmospheric CO2 increases faster eves as the ocean absorbs more carbon dioxide (no upwelling of CO 2 rich water in the Eastern Pacific). This means that the land biosphere mey become a net source of carbon in the greenhouse world.
Cox et al. 2000 (Nature)‫‏‬

Gas solubility in water


Solubility of any gas in water decreases with increasing temperature (the figure left is oxygen solubility). Partial pressure of a gas in solution in a given temperature is proportional to its concentration (Henry's law). The partial pressure of a gas in water changes with temperature proportional to exp(-1/T) (Van t'Hoff law). The gas flux across sea surface if proportional to the difference of partial pressures of the gas in water and air, multiplied by transfer velocity k and gas solubility α.

What does the transfer velocity k depend on?

Similarly as in the case of aerosol fluxes, there are many different parameterizations of k, most of them basing on wind speed U (see the figure above). W-92 jest przykładem zależności od U2 a “Eq. 4” od U3 – in fact both were proposed by the same author (Wannikhof 1992 & 1999).
Wannikhof & McGillis 1999 (Geophysical Res. Letters)‫‏‬

U2 or U3?

Wannikhof i McGillis 1999 proposed to parameterize k for CO2 with U3 instead of U2. More recent studies tend to prefer the older parameterization (U2). The future lies most probably with parameterizing it more directly with wave slopes measured by satellite radars (scatterometers) – see Frew et al. 2004, 2007
Wannikhof & McGillis 1999 (Geophysical Res. Letters)‫‏‬

In-water CO2 partial pressure for August.

CO2 flux across the sea surface depends on the difference of pCO2 between sea water and air. For in-water pCO2 < 380 μatm the flux goes from air to sea. Its value is proportional to the difference and to squared wind speed.
Takahashi et al. 2003 (Deep Sea Research)

CO2: average flux across the sea surface

Global flux: +2.2 Pg C yr-1 (+22%, -19%) for a non-El Niño year. The balance was made from 940.000 measurements of pCO2 partial pressure assuming the U2 parameterization (U3 gives flux values which are 70% greater).
Takahashi et al. 2003 (Deep Sea Research)

Seasonal changes of in-water pCO2

Positive numbers mean the pCO2 is larger in the warm season (physics dominates) while negative mean the maximum is in the cold season (biology dominates). Takahashi et al. 2003 (Deep Sea Research)

How does it work?
An example of seasonal changes of CO2 partial pressure and concentration in the Bermuda region: a) changes in sea surface temperature (SST) and measured CO 2 partial pressure. b) average value of pCO2 corrected to temperatuure using van 't Hoffa law (representing only temperature related changes) and pCO2 recalculated to a constant (average) SST (representing CO2 in-water concentration).

Takahashi et al. 2003 (Deep Sea Research)

CO2 concentration seasonal variability

Seasonal changes of pCO2 after correcting for temperature changes - which makes them proportional to actual in-water CO2concentration changes.
Takahashi et al. 2003 (Deep Sea Research)

Temperature induced pCO2 seasonal changes

Seasonal changes of in-water carbon dioxide partial pressure after subtracting biology related changes – leaving only the temperature related effect. Takahashi et al. 2003 (Deep Sea Research)

Biology “pump” and physically forced fluxes

Chisholm 2000 (Nature)

Summary 1/3
Atmospheric concentration of the main atmospheric greenhouse gas (except for H2O) increases every year due to over 6 Gt (Pg) carbon emission from the fossil fuel we burn, from concrete production (and possibly up to 2 Gt from forest clearing).  Ocean absorbs about 2 Gt C, land vegetation another 1 Gt C. The other > 3 Gt C stay in the Instrument setup for direct atmosphere, increasing CO2 concentration measurements of CO2 fluxes yearly by over 1.5 ppm (μatm) with “eddy  Since the preindustrial era, we increased correlation”methods – the future of gas flux ocean atmospheric CO2 from ~ 280 to over 380 ppm.


Interannual variability of CO2 sink is greater for the continents than for the oceans. Over the ENSO cycle the variability in land and sea have inverse signs.

CO2 : will we acidify the ocean?

a) Forecasted emission and concentration of CO2 and ocean pH b) Comparison of change rate in ocean pH in last glacial period (A), latest 300 M years (B), in historical times (C) and foretasted for this century (D).
K. Caldeira & M.E. Wickett, 2003, Nature 425, 325-325

CO2 i CH4 – how do they influence the climate?

Atmospheric concentration of methane is about 220 smaller that of carbon dioxide. However it's much greater greenhouse effect means that methane is responsible for about 20% of anthropogenic greenhouse effect.
NCR report 2006

Methane increase seems to slow down

As opposed to CO2 atmospheric concentration, methane increase seems to slow down in recent years (the figure shows concentration measurement series and calculated yearly increase). Studies of geographical gradients seem to suggest that the slow down in methane emission increase happens mostly in the Northern Hemisphere.
NOAA, updated with Dlugokencky et al. 2003 (Geophysical Res. Letters)

Methane balance – what we knew in early 2006

Methane fluxes are given in millions of tons per year.
Lowe 2006 (Nature)

Methane geography

Because most of the methane sources are located in the Northern Hemisphere, and its atmospheric lifetime is short (a few years) the concentration over Northern Hemisphere is always greater than over the Southern one. The seasonal changes are anti-correlated (obviously).


Methane geography: a model

In methane emission (and in its tropospheric concentration) the terrestrial sources are clearly dominating. In the stratosphere, methane lingers mostly in the tropics. The figure is a model result.


Methane geography: observations

Methane concentration from SCIAMACHY sensor of the ENVISAT satellite. The surprising fact is the very high concentration over tropical jungles. Recent laboratory studies (Keppler et al. 2006) confirm that deciduous (leafy) forests are a methane source (globally 63-243 M t / year !) .

Frankenberg et al. 2005 (Science)

Concentration of climate influencing gases 1978-2006


Anthropogenic radiation forcing 1979-2005


Summary 2/3
The next most important greenhouse gas is methane. Only about 10% is emitted from the ocean. Most is emitted from the land, especially in the Northern Hemisphere.  Its atmospheric concentration seems to stabilize in recent years.  The third most important greenhouse gas is nitrous oxide (N2O), produced CO is not the whole story: : atmospheric 2 mainly by agriculture and to a lesser concentrations of three other greenhouse gases (Shine & Sturges 2007) degree by combustion engines.

Climate importance of freons (mainly CFC-12 and CFC-11) is hopefully decreasing as they are not produced anymore. Freons and nitrous oxide have also a destructive influence on the ozone hole.

DMS and climate: the CLAW hypothesis

Since 1972 (Lovelock et al.), we know that one of the main sources of atmospheric sulfur is dimethyl sulfide (DMS) produced by phytoplankton Sulfur particles are condensation nuclei of aerosol and cloud droplets, cooling down the planet. In 1987 CLAW authors proposed a feedback mechanism by which phytoplankton controls the climate. CLAW = Charlson, Lovelock, Andreae & Warren 1987 (Nature)

DMS feedback mechanism discovered?

Bates, Charles & Gammon (1987) discovered a strong correlation between daily irradiance dose at the sea surface and DMS concentration which could be a confirmation of a crucial part of the postulated feedback mechanism.
Bates, Charles, Gammon 1987 (Nature)

Shipping: as important as phytoplankton?

The amount of sulfur emitted in engine exhaust by ocean going ships shows that in many basins (especially in the Northern Hemisphere) is larger than DMS derived sulfur . Global cooling radiative forcing (by cloud cover increase) created by shipping is estimated at -0.11 W/m2.

Capaldo et al. 1999 (Nature)

We and the phytoplankton: who produces how much?

Biogenic sources of sulfur (of which 90% is DMS) are responsible for 23% of emitted sulfur and 42% of atmospheric sulfur content. Anthropogenic sources are 70% of emission and 37% sulfur content in the atmosphere. Volcanoes are responsible for respectively, 7% and 18%.
Simó 2001 (Trends in Ecology and Evolution)

Problems of the CLAW hypothesis

The CLAW hypothesis does not make sense for the evolutionists: DMS producing species help also their competitors by cooling the planet. The competitors by not using energy for the effort would be the actual winners. DMS, and more correctly its precursor DMSP - of many biological uses, among others an antioxidant) (Sunda et al. 2002) is releases by organism mostly after their death.

DMS itself is a product of decomposition of DMSP, mostly by bacteria, which do not gain evolutionarily by cooling the planet.

Simó 2001 (Trends in Ecology and Evolution)

But still DMS strongly correlates with irradiance...

DMS concentration in surface waters correlates very strongly with the irradiance dose (left: r2=0.94 for the Mediterranean Sea; right r2=0.95 for the World Ocean). It can be explained in part by its antioxidant activity in the cells. However such a high correlation compared to such indirect link through the food chain is intriguing. Maybe there is a grain of truth in the CLAW...
Vallina & Simó 2007 (Science)

Summary 3/3

Over 40% of atmospheric sulfur, (cooling Earth by scattering the Solar radiation back to space and by increasing cloud albedo and coverage) is of biological origin, mostly from dimethyl sulfide (DMS) of oceanic origin.

In the 1980s, a hypothesis of natural temperature regulation by DMS producing Phytoplankton while producing phytoplankton has been proposed (CLAW DMSP, the DMS precursor ? hypothesis). (Fig. by. Mirka Ostrowska, IOPAN)  The hypothesis was criticized as evolutionary naive (plankton altruism).

DMS is not even a direct plankton product but rather of bacteria decomposition of its precursor (DMSP) released to the sea water only after the plankton cells are dead. However, DMS concentration is so strongly correlated with irradiance that it cannot be fully explained even by the photoprotective role of DMSP (an antioxidant).