Marine Chemistry II

Environmental Geochemistry
DM Sherman, University of Bristol

Carbonate Equilibria
and the pH of Seawater

The Global Carbon Cycle (in 1015 g)

Respiration (60)
Photosynthesis (120)

Oceans
Biosphere

(37000 as HCO3-)

(1600)
Riv
ers

0.2

(0.6

Volcanic Emission
(0.048-0.18)

CO2 Dissolution/Degassing (100)

Respiration (60)

Atmosphere (748 as CO2)

Soil (1200-1600)

Lithosphere (50 x 106 as CaCO3; 3870 as Oil/Gas/Coal)

Speciation of H2CO3

Open Carbonate System

(fixed PCO2= 10-3.5 bar)
CO2(g) + H2O = H2CO3

pK = 1.46

p H2CO3 = pK1+ pPCO2

(If pPCO2 = 3.5 then, pH2CO3 = 4.94)
H2CO3 +H2O = H3O+ + HCO3-

pK = 6.35

pHCO3- = pK2 + pH2CO3 - pH =11.29 - pH

HCO3- +H2O = H3O+ + (CO3)2-

pK = 10.33

p(CO3)2- = pK3 + pHCO3- - pH = 21.62 - 2pH

Resulting pH of Rain...
The charge-balance constraint [H+] = [HCO3-] +2[CO3-2]
gives pH pHCO3- = 5.6

Effect of CaCO3 (Calcite/Aragonite)

If the system is saturated in calcite, we
need the additional equilibrium:
CaCO3(s) = Ca2+ + (CO3)2-

pK = 8.48

pCa2+ = pK4- p(CO3)2- + 2pH

= -13.14 + 2pH
Charge-balance requires that
2[Ca] = 2[CO3-2] + [HCO3-] [HCO3-]
or pCa = pHCO3- + 0.301

pH of Seawater (Surface, pPCO2 = 3.5)

When pCa = pHCO3 + 0.301, pH = 8.3

Actually, its a bit more complicated..

When we include all of the other acid-base and ionpairing equilibria, we find that surface seawater
should have a pH near 7.8.
The observed surface pH = 8.3 is a consequence of
supersaturation of CaCO3 (SI = 1.2).
Presumably, supersaturation is favored by calcifying
organisms as it is easier to grow shells under such
conditions.

Predicted Changes in Oceanic pH

(Caldeira & Wickett 2003)

Biological Controls on Dissolved

Carbonate
i) CO2 consumption by photosynthesis:

CO2 + 2H2O CH2O + O2

ii)CO2 release (mineralization) by respiration

CH2O + O2 CO2 + 2H2O

(Note, the arrows indicate irreversible reactions!)
iii) Biomineralization of CO3-2

Ca+2 + CO3-2 = CaCO3(calcite)

CaCO3-Shelled Zooplankton
Foraminifera

Pteropods

Coccolithophorids
Single-celled phytoplankton with cell walls made of
CaCO3 (calcite). Large blooms dominate the ocean
surface.

Map of near-surface marine calcite (from NASA)

pH of Seawater vs. Depth

Photosynthesis increases pH:
H+ + HCO3- = CO2 + H2O
CO2 + H2O CH2O + O2

Respiration decreases pH:

CH2O + O2 CO2 + H2O
CO2 + H2O = H+ + HCO3-

Dissolution of CaCO3:
CaCO3 + H+ = Ca2+ + HCO3-

Alkalinity and Total Dissolved Carbon

Alkalinity is the capacity of a solution to neutralize
added acid.
Carbonate Alkalinity is
[Alk] = [HCO3-] + 2[CO3-2] + [OH-] - [H+]
Total Dissolved Inorganic Carbon (CO2) is
[HCO3-] + [CO3-2] + [H2CO3]

Effect of Photosynthesis
Photosynthesis will not affect alkalinity but will
increase the pH:
CO2 + H2O CH2O + O2
H2CO3 = CO2 + H2O
H+ + HCO3- = H2CO3
H+ + HCO3- CH2O + O2
The pH increase will favor pptn of CaCO3:
Ca+2 + HCO3- = CaCO3 + H+

Effect of Respiration
Respiration will not affect alkalinity but will decrease
pH:
CH2O + O2 CO2 + H2O
CO2 + H2O = H2CO3
H2CO3 = HCO3- + H+
CH2O + O2 H+ + HCO3The pH decrease will favor dissolution of CaCO3:
CaCO3 + H+ = Ca+2 + HCO3-

Effect of CaCO3 precipitation

HCO3- = H+ + CO3H+ + HCO3- = H2CO3
H2CO3 = CO2 + H2O
Ca+2 + CO3- CaCO3
Ca+2 + 2HCO3- CaCO3 + CO2 + H2O
Hence, pptn of CaCO3 actually releases CO2,
decreases the alkalinity, and decreases pH.

Shallow vs. Deep Ocean

Shallow vs. Deep Ocean

Surface Ocean

Downwelling
Upwelling

Deep Ocean

Sinking
Particles

Sinking calcite
shells and organic
matter provides a
one-way flux of C to
the deep ocean.
Oxidation of organic
C and dissolution of
CaCO3 will increase
CO2 in Deep
Ocean.

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Effect of Biological Processes

Photosynthesis

CaCO3 pptn

Distribution of Carbonate Sediments

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Carbonate Depth Profile (Mid Atlantic)

Surface waters are supersaturated with CaCO3.

Calcite Compensation Depth:

Dissolution Rate > Rain Rate

Deep waters are undersaturated with CaCO3.

CaCO3 saturation Depth

(Feely et al., 2004)

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Change in Alkalinity/TDC in Oceans

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Absorption of Atmospheric CO2 by the

Oceans
Atmospheric CO2

Gas Absorption
CO2 + H2O + CO3-2 = 2HCO3H+ + HCO3- CH2O + O2
Ca+2 + 2HCO3- = CaCO3 + CO2 + H2O

Upwelling

Shallow Ocean:
carbon fixing by photosynthesis.

Sinking of CH2O + CaCO3

CH2O + O2 H+ + HCO3-

Deep Ocean:
mineralization by respiration.

CaCO3 + H+ = Ca+2 + HCO3-

Summary
Equilibrium with atmospheric PCO2 = 10-3.5 bar and
saturation in CaCO3 buffers the pH of seawater to 8.3.
CO2 is sequestered in the deep ocean by the biological
pump.
Surface waters are supersaturated in calcite; deep
waters are undersaturated. The carbonate
compensation depth reflects the competition between the
kinetics of dissolution and the downward flux of
particulate CaCO3.

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Box Model for Oceans

Surface Ocean

Indian

Pacific

Atlantic

Southern

Primary Productivity

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