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.

oceanworld.tamu.edu
 IPCC report: what we knew in 2007

Dod

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, http://cdiac.esd.ornl.gov/trends/co2/sio-mlo.htm)
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.
NOAA, http://www.esrl.noaa.gov/gmd/ccgg/trends/
 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

Aero

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

atmosphere, increasing CO2 concentration Instrument setup for direct
yearly by over 1.5 ppm (μatm) measurements of CO2 fluxes
with “eddy
 Since the preindustrial era, we increased correlation”methods – the
atmospheric CO2 from ~ 280 to over 380 ppm. future of gas flux ocean
measurements.
 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).
NOAA
 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.

NOAA
 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

NOAA
Anthropogenic radiation forcing 1979-2005

NOAA
 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
degree by combustion engines. gases (Shine & Sturges 2007)

 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 has been proposed (CLAW Phytoplankton while producing
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).