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Environmental Geochemistry
DM Sherman, University of Bristol
Carbonate Equilibria
and the pH of Seawater
Respiration (60)
Photosynthesis (120)
Oceans
Biosphere
(37000 as HCO3-)
(1600)
Riv
ers
0.2
(0.6
Volcanic Emission
(0.048-0.18)
Respiration (60)
Soil (1200-1600)
Speciation of H2CO3
pK = 1.46
pK = 6.35
pK = 10.33
Resulting pH of Rain...
The charge-balance constraint [H+] = [HCO3-] +2[CO3-2]
gives pH pHCO3- = 5.6
pK = 8.48
CaCO3-Shelled Zooplankton
Foraminifera
Pteropods
Coccolithophorids
Single-celled phytoplankton with cell walls made of
CaCO3 (calcite). Large blooms dominate the ocean
surface.
Dissolution of CaCO3:
CaCO3 + H+ = Ca2+ + HCO3-
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-
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.
10
Photosynthesis
CaCO3 pptn
11
12
13
Gas Absorption
CO2 + H2O + CO3-2 = 2HCO3H+ + HCO3- CH2O + O2
Ca+2 + 2HCO3- = CaCO3 + CO2 + H2O
Upwelling
Shallow Ocean:
carbon fixing by photosynthesis.
CH2O + O2 H+ + HCO3-
Deep Ocean:
mineralization by respiration.
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.
14
Indian
Pacific
Atlantic
Southern
Primary Productivity
15