Today, the atmosphere contains 78% N
2, 21%
O
2, and 0.036% CO
2 by volume, and is strongly oxidizing. All of the molecular oxygen present
in the Earth’s atmosphere has been produced as the result of oxygenic photosynthesis, the
source of the original O
2 being photosynthetic activity in the primordial oceans.
The development
of aquatic photosynthesis coincided with a long and reasonably steady drawdown of atmospheric
CO
2, from concentration approximately 100-fold higher than in the present-day atmosphere to
approximately half of the present levels. This drawdown was accompanied by a simultaneous evolution
of oxygen from nil to approximately 21%, comparable to that of the present day. The current
atmospheric oxygen concentration is maintained in equilibrium between the production by photosynthesis
and the consumption by respiration, with annual fluctuations of ±0.002%. Over geological
time scales, the drawdown of CO
2 was not stoichiometrically proportional to the accumulation
of O
2 because photosynthesis and respiration are but two of the many biological and chemical
processes that affect the atmospheric concentrations of these two gases. The removal rate of
CO
2 from the atmosphere by photosynthesis on land is about 60 gigatons C yr
-1, worldwide.
The concentration of oxygen in the oceans (85.8%) is influenced horizontally and vertically by
physical features such as the thermocline (i.e., a layer in a large body of water, such as a lake,
that sharply separates regions differing in temperature), which isolates deep water from exchange
with the atmosphere and can be a zone of significant decomposition causing an oxygen minimum.
Oxygen is only sparingly soluble in water (oxygen solubility is inversely proportional to the temperature)
and diffuses about 104 times more slowly in water than air. Deep water masses are produced
at the sea surface in the polar zones where cooling gives rise to increased gas solubility
and convection currents. These waters remain largely intact and move through the ocean basins
with their oxygen concentration decreasing with time due to the decomposition of organic matter.
Carbon, the key element of all life on Earth, has a complex global cycle that involves both physical
and biological processes, made up of carbon flows passing back and forth among four main
natural reservoirs of stored carbon: the atmosphere, storing 735 gigatons (0.001%) of the
world’s carbon as carbon dioxide (CO2), carbon monoxide (CO), methane (CH4), longer chain
volatile hydrocarbons, and halogen compounds (CFC and HCFC compounds); living organisms,
storing 8000 gigatons (0.001%) of the world’s carbon as compounds like fats, carbohydrates,
and proteins; the hydrosphere, storing 39,000 gigatons (0.06%) of the world’s carbon, as dissolved
carbon dioxide; the lithosphere, storing 1000 gigatons (0.002%) of the world’s carbon in the form of
fossils (e.g., oil, natural gas, lignite, and coal), and 62,000,000 gigatons (99.9%) in sedimentary
rocks (e.g., limestone and dolomite). Carbon is also present in the mineral soil, in the bottom sediments
of water bodies, in peat, bogs and mires, in the litter and humus, which contain 3000 gigatons
(0.005%) of the world’s carbon. |
|
Carbon dioxide enters the ocean from the atmosphere because it is highly soluble in water; in
the sea, free dissolved CO
2 combines with water and ionizes to form bicarbonate and carbonate
ions, according to the following equilibrium:
CO
2 + H
2O ↔ H
2CO
3 ↔ HCO
-3 + H
+ ↔ CO
2-3 + H
+ ↔ HCO
-3 ↔ CO
2 + OH
- (4.7)
These ions are bound forms of carbon dioxide, and they (especially bicarbonate) represent
by far the greatest proportion of dissolved carbon dioxide in seawater. On average, there
are about 45 ml of total CO
2 in 1L of seawater, but because of the equilibrium of chemical
reactions, nearly all of this occurs as bound bicarbonate and carbonate ions which thus act
as a reservoir of free CO
2. The amount of dissolved CO
2 occurring as gas in 1L of seawater is
about 0.23 ml. When free CO
2 is removed by photosynthesis, the reaction shifts to the left and
the bound ionic forms release more free CO
2; so even when there is a lot of photosynthesis,
carbon dioxide is never a limiting factor to plant production. Conversely, when CO
2 is released
by the respiration of algae, plants, bacteria, and animals, more bicarbonate and carbonate ions
are produced.
According to the general chemical reactions presented earlier, the pH of seawater is largely
regulated by the concentrations of bicarbonate and carbonate, and the pH is usually 8±0.5. The
seawater acts as a buffered solution, because when CO
2 is added to seawater due to mineralization
processes and respiration, the number of hydrogen ions increases and the pH goes down (the
solution becomes more acidic). If CO
2 is removed from water by photosynthesis, the reverse
happens and the pH is elevated.
Some marine organisms combine calcium with carbonate ions in the process of calcification to
manufacture calcareous skeletal material. The calcium carbonate (CaCO3) may either be in the
form of calcite or aragonite, the latter being a more soluble form. After death, this skeletal material
sinks and is either dissolved, in which case CO
2 is again released into the water, or it becomes
buried in sediments, in which case the bound CO
2 is removed from the carbon cycle. The
amount of CO
2 taken up in the carbonate skeletons of marine organisms has been, over geological
time, the largest mechanism for absorbing CO
2. At present, it is estimated that about 50 x 10
15 tons
of CO
2 occurs as limestone, 12 x 10
15 tons in organic sediments, and 38 x 10
12 tons as dissolved
inorganic carbonate.
Calcification is not confined to a specific phylogenetically distinct group of organisms, but
evolved (apparently independently) several times in marine organisms. Carbonate sediments
blanket much of the Atlantic Basin, and are formed from the shells of both coccolithophorids
and foraminifera. As the crystal structures of the carbonates in both groups is calcite (as
opposed to the more diagenically susceptible aragonite), the preservation of these minerals and
their co-precipitating trace elements provides an invaluable record of ocean history. Although on
geological time scales, huge amounts of carbon are stored in the lithosphere as carbonates, on ecological
time scales, carbonate formation depletes the oceans of Ca
2+, and in so doing, potentiates
the efflux of CO
2 from the oceans to the atmosphere. This calcification process can be summarized
by the following reaction:
Ca
2+ + 2HCO
-3 ↔ CaCO
3 + CO
2 + H
2O (4.8)
Among the marine organisms responsible for calcification, coccolithophores play a major role,
especially Emiliania huxleyi. When the blooms of this Haptophyta appear over large expanses of
the ocean (white water phenomenon), myriad effects on the water and on the atmosphere above
can be observed. Although each cell is invisibly small, there can be as many as a thousand billion
billion (10
21) of them in a large bloom, and the population as a whole has an enormous impact.
E.
huxley blooms are processed through the food web, with viruses, bacteria, and zooplankton all contributing
to the demise and decomposition of blooms. Some debris from the bloom survive to sink
to the ocean floor, taking chemicals out of the water column. While they live and when they die, the
phytoplankton cells leak chemicals into the water. A bloom can be thought of as a massive chemical
factory, extracting dissolved carbon dioxide, nitrate, phosphate, etc. from the water, and at the same
time injecting other chemicals such as oxygen, ammonia, DMS, and other dissolved organic compounds
into the water. At the same time, the chemical factory pumps large volumes of organic
matter and calcium carbonate into the deep ocean and to the ocean floor. Some of this calcium carbonate
eventually ends up as chalk or limestone marine sedimentary rocks, perhaps to cycle through
the Earth’s crust and to reappear millions of years later as mountains, hills, and cliffs. Coccolithophorids
are primarily found at low abundance in tropical and subtropical seas, and at higher
concentrations at high latitudes in midsummer, following diatom blooms. Hence, export of
inorganic carbon by diatoms in spring at high latitudes can be offset by an efflux of carbon to
the atmosphere with the formation of coccolithophore blooms later in the year.
The contemporary ocean export of organic carbon to the interior is often associated with diatom
blooms. This group has only risen to prominence over the past 40 million years.
Coccolithophorid abundance generally increases through the Mesozoic, and undergoes a
culling at the Kretaceous/Tertiari (K/T) boundary, followed by numerous alterations in the Cenozoic.
The changes in the coccolithophorid abundances appear to trace eustatic sea level variations,
suggesting that transgressions lead to higher calcium carbonate fluxes. In contrast, diatom sedimentation
increases with regressions and because of the K/T impact, diatoms have generally replaced
coccolithophorids as ecologically important eukaryotic phytoplankton. On much finer time scales,
during the Pleistocene, it would appear that interglacial periods favor coccolithophorids abundance,
whereas glacial periods favor diatoms. The factors that lead to glacial-interglacial variations
between these two functional groups are relevant to elucidating their distributions in the contemporary
ecological setting of the ocean.
Coccolithophores influence regional and global temperature, because they can affect ocean
albedo and ocean heat retention, and have a greenhouse effect. Coccoliths do not absorb
photons, but they are still optically important because they act like tiny reflecting surfaces, diffusely
reflecting the photons.
A typical coccolith bloom (containing 100 mg m
-3 of calcite carbon) can increase the ocean
albedo from 7.5 to 9.7%. If each bloom is assumed to persist for about a month, then an annual
coverage of 1.4 x 10
6 km
2 will increase the global annual average planetary albedo by
where 510 x 10
6 km
2 is the surface area of the Earth.
This is a lower bound on the total impact, because sub-bloom concentration coccolith light scattering
will have an impact, over much larger areas (estimated maximum albedo impact = 0.21%).
A 0.001% albedo change corresponds to a 0.002 W m
-2 reduction in incoming solar energy,
whereas an albedo change of 0.21% causes a reduction of 0.35 W m
-2. These two numbers can
be compared to the forcing due to anthropogenic addition of CO
2 since the 1700s, estimated to
be about 2.5 W m
-2. Coccolith light scattering is therefore a factor of only secondary importance
in the radiative budget of the Earth. However, the scattering caused by coccoliths causes more heat
and light than usual to be pushed back into the atmosphere; it causes more of the remaining heat to
be trapped near to the ocean surface, and only allows a much smaller fraction of the total heat to
penetrate deeper in the water. Because it is the near-surface water that exchanges heat with the
atmosphere, all three of the effects just described conspire to mean that coccolithophore
blooms may tend to make the overall water column dramatically cooler over an extended
period, even though this may initially be masked by a warming of the surface skin of the ocean
(the top few meters).
All phytoplankton growth removes CO
2 into organic matter and reduces atmospheric CO
2 (by means of photosynthesis). However, coccolithophores are unique in that they also take up
bicarbonate, with which to form the calcium carbonate of their coccoliths (calcification process).
The coccolithophorid blooms are responsible for up to 80% of surface ocean calcification. In the
equilibrium of calcification process, an increase in CO
2 concentration leads to calcium carbonate
dissolution, whereas a decrease in CO
2 levels achieves the reverse. While photosynthetic carbon
fixation decreases the partial pressure of CO
2 as dissolved inorganic carbon is being utilized,
conditions favoring surface calcification by coccolithophorid blooms contribute to the increase
of dissolved CO
2.
The relative abundance of the components of the carbonate system (CO
2, H
2CO
3, HCO
-3 ,and CO
2-3) depends on pH, dissolved inorganic carbon, and the total alkalinity, and the equilibrium
between the components can shift very easily from being in one of these dissolved
forms to being in another. How much of the total carbon in each form is determined
mainly by the alkalinity and by the water temperature? When the seawater carbon system
is perturbed by coccolithophore cells removing HCO
-3 to form coccoliths, this causes a rearrangement of how much carbon is in each dissolved form, and this rearrangement takes
place more or less instantaneously. The removal of two molecules of HCO
-3 and the addition of one molecule of CO
2 change the alkalinity and this indirectly causes more of the dissolved
carbon to be pushed into the CO
2 form. Although the total dissolved carbon is obviously
reduced by the removal of dissolved carbon (bicarbonate ions) into solid calcium carbonate,
yet the total effect, paradoxically, is to produce more dissolved CO
2 in the water. In this
way, coccolithophore blooms tend to exacerbate global warming by causing increased atmospheric
CO
2 (greenhouse effect), rather than to ameliorate it, as is the case when dissolved CO
2 goes into new organic biomass. However, recent work is showing that additional properties of
coccoliths may make the situation yet more complicated. Coccolith calcite is rather dense
(2.7 kg L
-1 compared to seawater density of 1.024 kg L
-1), and the presence of coccoliths in
zooplankton faecal pellets and marine snow (the two main forms in which biogenic matter
sinks to the deep ocean) causes them to sink more rapidly. Slow-sinking organic matter
may also adhere to the surfaces of coccoliths, hitching a fast ride out of the surface waters.
If organic matter sinks faster then there is less time for it to be attacked by bacteria and
so more of the locked-in carbon will be able to escape from the surface waters, depleting
the surface CO
2. Probably this co-transport of organic matter with coccoliths offsets the atmospheric
CO
2 increase that would otherwise be caused, and makes coccolithophore blooms act to
oppose global warming, rather than to intensify it.