Chapter 5

Carbon Dioxide in Natural Waters

1 Dissolution and Dissociation of CO2 in Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124

1.1 Simple CO2 -Water System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
1.2 Dissolved Inorganic Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
1.3 CO2 and the pH of Fresh and Sea Waters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
2 CO2 Transfer from Atmosphere to Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
2.1 Industrial-Age Increase in Atmospheric CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
2.2 Partitioning of CO2 between Atmosphere and Water . . . . . . . . . . . . . . . . . . . . . . 134
3 Calcite and Aragonite in Natural Waters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
4 Degree of Saturation with Respect to Carbonate Minerals . . . . . . . . . . . . . . . . . . . . . . . 138
4.1 Rivers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
4.2 Ocean Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
5 CO2 Phases: Gas, Liquid, Hydrate, Ice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
5.1 Phase Diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
5.2 CO2 in Oceanic Water Column and Continental Crust . . . . . . . . . . . . . . . . . . . . . 144
6 Air-Sea CO2 Exchange due to Carbonate and Organic Carbon Formation . . . . . . . . . 148
6.1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
6.2 CO2 Emission: General Case . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
6.3 Carbonate Precipitation at a Fixed Atmospheric CO2 . . . . . . . . . . . . . . . . . . . . . . 154
6.4 Rising Atmospheric CO2 due to Carbonate Precipitation . . . . . . . . . . . . . . . . . . 158
6.5 Controls on the Sea-Air CO2 Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159

This chapter presents some of the basic physical and chemical relationships that are
relevant to an understanding of the behavior of CO2 in the Earth’s surface environment.
It would be an understatement to say that the literature on this subject is extensive—it
is prodigious! In Chapter 2 we dealt with the Earth’s atmosphere in the past and present
that is based mostly on the model of an ideal gas. However, CO2 on the Earth’s surface
interacts with other gases, it dissolves in water, and reacts with water, other dissolved
species, and minerals. Many of the chemical reactions involving CO2 are either directly
or indirectly mediated by biological processes, as is briefly discussed in Chapter 1 and
further addressed in Chapters 6 and 9. This chapter deals with some of those funda-
mental aspects of CO2 and oceanic and continental waters that are reasonably closely
related to the global-scale natural systems and processes, and it includes the following
subjects: dissolution of CO2 in water at the Earth’s surface conditions; a summary of
chemical thermodynamic equilibrium relationships; transfer of CO2 between atmo-
sphere and water, and the rising atmospheric CO2 concentration; solubilities of calcite
and aragonite and the saturation of natural waters with respect to these minerals; CO2
123
124 carbon in the geobiosphere—earth’s outer shell

in the liquid and hydrate phases as related to the potential disposal of industrial CO2
in the deep ocean; and sea-air exchange of CO2 due to the formation and storage of
calcium carbonate and organic carbon in sediments.

1 Dissolution and Dissociation of CO2 in Water

1.1 Simple CO2 -Water System

Dissolution of carbon dioxide in water is the first step that enables photosynthetic
production of organic matter in aquatic systems, precipitation of carbonate minerals,
and chemical weathering of the Earth’s crust and sediments. Carbon dioxide dissolves
in water and reacts with it producing negatively charged bicarbonate and carbonate
ions, the electric charges of which are balanced in pure water by the hydrogen ion
or in a natural solution by other metal cations and the hydrogen ion. Dissolution and
dissociation of the gaseous species CO2 (g) in water are represented by the following
reactions:

CO2 (g) = CO2 (aq) (5.1)

CO2 (aq) + H2 O = H + HCO− 3
+
(5.2)
HCO− 3 = H +
+ CO 2−
3 (5.3)

The aqueous uncharged CO2 includes the species H2 CO3 that constitutes only a
small fraction, about 1/400, of CO2 in solution. Alternative use of either CO2 or H2 CO3
for all of the aqueous species CO2 (aq) is acceptable without a loss of correct meaning
(e.g., Millero, 1996). Because of the formation of the aqueous ions HCO− 3 and CO3
2−

from CO2 in solution, the total concentration of dissolved inorganic carbon is the sum
of all the carbon species, CO2 (aq), HCO− 2−
3 , and CO3 . This parameter is also called
dissolved inorganic carbon, to distinguish it from dissolved organic compounds, and it
is usually denoted CO2 or DIC:

DIC = CO2 (aq) + HCO−

3 + CO3
2−
(mol kg−1 ) (5.4)

Concentration units of DIC in mols of carbon per 1 kg solution—that is, 1 kg of

solution consisting of water and dissolved species—are conventionally and widely
used for natural waters1 .
In this chapter relationships in the CO2 -carbonic acid-carbonate system are mainly
described in terms of apparent or stoichiometric constants that are dependent not only
on temperature and pressure, as are true thermodynamic equilibrium constants, but
also on composition (e.g., salinity). In addition, detailed carbon system calculations

1 The units of DIC and of the CO2 solubility, and dissociation constants K that are given in (5.4)–(5.6), can
be converted to molal concentrations, in units of mols per 1 kg H2 O. For a solution of known composition, a
value in mol/kg solution divided by a fraction (1 − kg of solutes in 1 kg solution) converts the concentration
to mols per 1 kg H2 O. It may also be noted that the units of ppm, parts per million, are mass/mass, such as
milligrams per 1 kg solution. Molar concentrations are in mol/liter, making them temperature dependent,
and for their conversion to mass/mass units the density of the solution must be known.