Chapter 1

The Carbonate System in Marine Environments

EJ. Millero

1.1
Introduction

The major portion of carbon in the oceans occurs in the carbonate system. This sys-
tem involves the following equilibria

(1.1)

Ca 2 + + CO~- ~ CaC0 3 (s) (1.4)

The carbonate system is very important since it regulates the pH of sea water, and
controls the circulation of CO 2 between the biosphere, the lithosphere, the atmosphere
and the oceans. Recent interest in the carbonate system in the oceans has resulted from
the "greenhouse effect" of CO 2 , The concentration of CO 2 in the atmosphere has in-
creased in the twentieth century (Fig. 1.1) (Keeling and Whorf 1994; Neftel et al. 1994
Since CO 2 can absorb infrared (IR) energy, this increase may cause the temperature
of the earth to increase and could eventually melt the polar ice caps. The increase in
CO 2 is related to the burning of fossil fuels (coal, petroleum and natural gas) and the
production of cement. The atmospheric CO 2 enters the oceans across the air-sea in-
terface and participates in the equilibrium processes outlined by Eq. 1.1 to 1.4. It also
can be used by ocean plants in primary productivity

The adsorption of CO 2 by the oceans is quite complicated, since the rates of move-
ment of the gas across the interface and from surface to deep waters varies with lati-
tude, time, and season. Diurnal and seasonal variations in the carbonate system are
caused by the removal of CO 2 by photosynthesis and solar heating. If the oceans were
well-mixed and in equilibrium with the atmosphere, most of the increased CO 2 would
be absorbed. This, however, is not the case, and the ocean response to increases in CO 2
is slow due to physical and chemical factors. The exchange involves the hydration of
CO 2, which is a slow process relative to ionization. Approximate time scales for the
mixing process can be determined using radioactive tracers to gain some idea of the
mixing times. To use these estimates it is necessary to have some idea of the total car-

A. Gianguzza et al. (eds.), Chemical Processes in Marine Environments

© Springer-Verlag Berlin Heidelberg 2000
10 F.J. Millero

350

340
• Icecores
330 0 Atmosphere

320
E
! 310

! 300

290

280

270
••••
1720 1760 1800 1840 1880 1920 1960 2000
Year

Fig. 1.1. The increase of CO 2 in the atmosphere with time (Keeling and Whorf 1994; Neftel et al. 1994)

Fossil fuel Atmosphere

WeatherinQ
747

I
Forestry

54.3
5.3 0.3 0.3 80

r
Land

-_
639
River Surface ocean
Soil DIC 1000
1625 DIC 0.45 DOC 17
....__.....__..._..__.......__.....__....._-_............._-_.......__.......__.....__...._...._-_......... ....._-_....._-_.....__....._-_.....__.......-

Pycnocline 32 Plankton - 5-27

....__.......__....•__.....__........._....__....._---.....---...---.....---..--.....-..---.... ~,- ..........._........._....._--_.....__.....__......

Deep waters
DIC36700 POC 7-9
POe 4.7 PIC 0.75
DOC 1198
Stocks (Gt C)
PIC 0.15
Flows (GtCyrl) POC 0.04

Sediments
POe 6000000
PIC 14000000

Fig. 1.2. The global carbon cycle (Millero 1996)