The Seawater CO2-Carbonate System

Close-up of Oolitic
http://en.wikipedia.org/wiki/File:CarmelOoids.jpg
Carmel formation, Utah, Jurassic
limestone
Some of the major geochemical roles of
the CO2 system in seawater include:
• seawater pH control and buffering
• source of carbon for photosynthesis
• long-term sink for carbon via carbonate precipitation and
subsequent burial and preservation of limestone and
dolomite
• formation of carbonate reefs
• exchange of CO2 with the atmosphere: CO2 is a major
greenhouse gas. Oceans are both a source and sink for atmospheric CO2
depending on location; a net sink overall.
• source of biogenic carbonates that are important
paleoindicators for a variety of parameters
The Seawater CO2-Carbonate System

Use of sign inspired by talk given by Andrew Dickson, a noted

CO2-system chemist from Scripps.
 The Seawater CO2-Carbonate System

The carbonate system is one of the most important chemical

and biogeochemical systems on earth.

Air Proton #1 Proton #2

CO2 (g)

Sea CO2 (aq) + H2O <=> H2CO3 <=> H+ + HCO3- <=> H+ + CO32-
Ko K1 K2

For seawater with a salinity of 35 and a temperature of 25 oC:

pKo = 1.547
pK1 = 5.847 (From Millero, Table 7.4)
pK2 = 8.915
O=C-OH
Structures of CO2 gas O=C=O
and bicarbonate ion HCO3- O-
CO2
H2CO3
The total
H2O + CO2 CO2 stays
constant
Equivalence points but the
speciation
depends
on pH

pH = pK1 pH = pK2

From, Millero, Chemical Oceanography, 1996. p 246

Terminology related to the CO2 system in
seawater
DIC - Dissolved inorganic carbon (CO2(g)+H2CO3+HCO3-+CO32-)
CO2 (g) : gaseous CO2
CO2 (aq) : gaseous CO2 that is dissolved in water
Carbonate ion: CO32-
Bicarbonate ion: HCO3-
Carbonic acid: H2CO3 (non-charged,neutral species)
Total CO2 (CO2): Sum of all dissolved components
of inorganic carbon, including CO2 (aq), H2CO3, HCO3-,
and CO32-. Total CO2 = DIC
PIC – Particulate inorganic carbon (calcite & aragonite minerals)
Distribution of DIC in the ocean- Vertical and
horizontal distributions

Total DIC (=Total CO2)

is lowest (but not
zero!) in surface
waters and is enriched
in deeper water - the
enrichment is greatest
in the deep Pacific due
to water mass age.

Why is this pattern

observed?
 Oceanic carbon cycle

Below saturation levels:

- CaCO3 decreases due to dissolution
- increases due to settling
 Depth at which CaCO3 is not preserved:
Diansyah, 2013 CCD (Carbonate Compensation Depth)
pH in Seawater – Complex control by CO2
system and Alkalinity

Dissolution of CO2 in water results in formation of

carbonic acid, which dissociates to yield bicarbonate
and carbonate plus protons.

CO2 (aq) + H2O <=> H2CO3 <=> H+ + HCO3- <=> H+ + CO32-

Thus, the addition of CO2 to water increases the {H+}

and therefore lowers the pH of the solution.
Conversely, removal of CO2 from solution removes
{H+} and increases the pH
Biological uptake of carbon by marine plants is mainly
as CO2(g) or H2CO3 i.e. neutral species. (some
phytoplankton can take up HCO3- and convert it to CO2 via carbonic anhydrase)

The uptake of CO2 (g) by photosynthetic organisms (or

chemosynthetic organisms) will raise the pH of the
system due to shift in the equilibria to the left (in the
direction consuming H+. Conversely, respiration of
organic matter reverses the cycle and liberates CO2
which will dissociate and lower the pH (increase {H+}).

CO2 (aq) + H2O <=> H2CO3 <=> H+ + HCO3- <=> H+ + CO32-

Remove CO2, consume H+ and raise pH

Add CO2, add H+ and lower pH

Vertical distribution of pH in the ocean

pH There is an ocean-
7.5 7.7 7.9 8.1 wide pH minimum
0 starting just below the
euphotic zone and
Depth (km)

2 extending to 500-1000
m. pH is lower in
Atlantic
deep Pacific than in
4 Pacific
Atlantic - due to water
mass age and
6 accumulation of
Indian respired CO2!
pH control in sea water - seawater pH varies from 7.9-8.4 with
an average between 8.1 and 8.2.

Seawater pH is controlled largely by the reaction:

HCO3- <=> H+ + CO32-

2
The equilibrium expression for this {H  }{CO3 }
Ka  
reaction is: {HCO3 }
where Ka is the dissociation constant of the bicarbonate. (~10-8.9) i.e. pKa ~8.9

Looking at this equilibrium expression another way, the pH will depend on the
ratio of bicarbonate to carbonate 
 K {HCO 3 }
and vice versa. {H }  a
2
{CO3 }

Measurement of seawater pH is not straightforward due to the complexity of the solution

and its ionic strength (I=0.7). Several different pH scales are in use (depending on
buffers used for standards). The NBS pH scale is the most common.
Ken Caldeira
Climate System Modeling Group
Lawrence Livermore National Laboratory
7000 East Avenue, L-103
Livermore, CA 94550, U.S.A.
E-mail: kenc@LLNL.gov
Robert Berner
Department of Geology and Geophysics
Yale University
New Haven, CT 06520-8109, U.S.A.
E-mail: berner@hess.geology.yale.edu

http://www.sciencemag.org/cgi/con
tent/full/286/5447/2043a
Precipitation and dissolution of carbonate
minerals in the ocean

All seawater contains the ions

Ca2+, CO32- and HCO3-. The
effective concentrations (i.e.
activities) of these species,
together with the pH,
temperature, pressure and ionic
strength determine whether the Cocolithophore
Emiliania huxleyi a
solution is saturated or haptophyte
phytoplankter secretes
undersaturated with respect to plates (liths) of calcite
(CaCO3)
CaCO3 minerals.
 Carbonate Minerals
Calcite
CaCO3 <=> Ca2+ + CO32- Ksp = 4.47 x 10-9 @ 25oC and Ionic
strength of 0 (a std condition)

Aragonite
CaCO3 <=> Ca2+ + CO32- Ksp = 6.02 x10-9 @ 25oC and Ionic
strength of 0 (a std condition)

Aragonite has the larger Ksp, therefore it is more soluble.

Aragonite is more amorphous (less

ordered crystal) and is more soluble
than calcite. These two compounds
differ only in their crystalline structure
not their chemical formula which is
CaCO3 in both cases.
Calcite is the predominant
form of CaCO3 in the Coccolithophore Foraminiferan
ocean and it is more stable
than aragonite
(amorphous CaCO3).

The organisms that

precipitate calcite include
(Cocolithophores and
foraminifera).

Organisms that precipitate

aragonite include Corals &
Pteropods. Dinoflagellate
Pteropod cyst
Despite surface supersaturation, spontaneous precipitation
of calcite or aragonite in surface waters does not occur
(except at very high pH's) due partly to interaction of Mg2+ with
CaCO3 crystal surfaces.

Only in very warm, saline waters

where CO2 solubility is low (hence
CO2 is low) will CaCO3 ppt out as
aragonite without biocatalysis.

Carbonate Ooids are examples of

spontaneously precipitated
carbonates – currently found on
Bahamas platform – but extensive http://www.iun.edu/~geos/

geological deposits exist

Calcifying organisms overcome the Mg2+ problem with enzymes and
intracellular compartmentalization of pH etc.
CaCO3 is not found in the surficial sediments in the
deepest parts of the sea (> ~5000 m) to any great
extent for at least two reasons.
1) The solubility of CaCO3 increases as Pressure  and as Temp. 

2) pH decreases with depth and more CaCO3 will dissolve.

The lysocline is the depth at which significant dissolution

of calcite begins. This depth is different for different ocean
water masses.

The CCD (Calcite compensation depth) is the depth at

which the dissolution of CaCO3 minerals equals the
supply rate (rain rate). No significant accumulation of
CaCO3 occurs below this depth.
Δ

Emerson and
Hedges Fig 12.12
 Places where CaCO3
CaCO3 dominates the sediments
are relatively shallow (<
5000 m)
CaCO3

CaCO3
CaCO3
CaCO3
CaCO3
CaCO3
CaCO3

Source: Open University: Ocean chemistry and deep sea sediments

pH control in sea water - seawater pH varies from 7.9-8.4 with
an average between 8.1 and 8.2.

Seawater pH is controlled largely by the reaction:

HCO3- <=> H+ + CO32-

2
The equilibrium expression for this {H  }{CO3 }
Ka  
reaction is: {HCO3 }
where Ka is the dissociation constant of the bicarbonate. (~10-8.9) i.e. pKa ~8.9

Looking at this equilibrium expression another way, the pH will depend on the
ratio of bicarbonate to carbonate 
 K {HCO 3 }
and vice versa. {H }  a
2
{CO3 }

Measurement of seawater pH is not straightforward due to the complexity of the solution

and its ionic strength (I=0.7). Several different pH scales are in use (depending on
buffers used for standards). The NBS pH scale is the most common.
Ken Caldeira
Climate System Modeling Group
Lawrence Livermore National Laboratory
7000 East Avenue, L-103
Livermore, CA 94550, U.S.A.
E-mail: kenc@LLNL.gov
Robert Berner
Department of Geology and Geophysics
Yale University
New Haven, CT 06520-8109, U.S.A.
E-mail: berner@hess.geology.yale.edu

http://www.sciencemag.org/cgi/con
tent/full/286/5447/2043a