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Table 19.1 Average changes to ocean chemistry and pH based on ocean carbon models and surface-
ocean measurements (modified from The Royal Society 2005 )
Preindustrial Today
2
preindustrial 3
preindustrial 4
preindustrial
CO 2atm (ppm)
280
380
560
840
1,120
mol kg 1 )
H 2 CO 3 (
m
9
13
19
28
38
mol kg 1 ) 1,768
HCO 3 ¯(
m
1,867
1,976
2,070
2,123
CO 3 2 ¯(
mol kg 1 )
m
225
185
141
103
81
Total DIC
(
2,003
2,065
2,136
2,201
2,242
mol kg 1 )
m
Mean surface pH
8.18
8.07
7.92
7.77
7.65
Ω calcite
5.3
4.4
3.3
2.4
1.9
Ω aragonite
3.4
2.8
2.1
1.6
1.2
et al. 2009 ), and the seawater carbonate chemistry is governed by a series of
chemical reactions that are in equilibrium (see also Chap. 2 by G´mez and
Huovinen and Chap. 4 by Gordillo):
CO 2 ð atoms Þ $ CO 2 ð aq Þ þ H 2 O $ H 2 CO 3 $ H þ þ HCO 3 $ 2H þ þ CO 2 3
CO 2 reacts with H 2 O causing the equilibrium to shift such that the concentration
of the bicarbonate ion (HCO 3 ¯) and carbonic acid (H 2 CO 3 ) increases, while that of
carbonate ions (CO 3 2 ¯) declines. The increase in hydrogen ion concentration lowers
pH because pH
-log 10 [H + ]. The mean surface ocean pH has already decreased
by 0.1 unit (equivalent to a 30% increase in H + ) from ~8.18 at the beginning of the
industrial revolution. For surface seawater with pH of ~8.07, approximately 91% of
the inorganic carbon is HCO 3 ¯, 8% CO 3 2 ¯, and only 1% CO 2(aq) . By 2100,
concentrations of CO 2(aq) and HCO 3 ¯ are predicted to increase by 192% and 14%,
respectively, and CO 3 2 ¯ decrease by 56%, with a concomitant decline in pH to 7.65
(The Royal Society 2005 ). Aside from the decline in carbonate concentration, a
reduction in the saturation state of aragonite and calcite is also predicted
(Table 19.1 ). As the seawater saturation state for a mineral measures its thermody-
namic potential to form or to dissolve, a reduction will make calcified structures
more vulnerable to erosion.
Carbonate ions play an important role in the formation of calcareous “skeletons”
for a large number of phototrophic marine organisms including corals, phytoplank-
ton, and macroalgae. If mitigation of emissions does not occur, CO 2 concentrations
could reach
¼
800 ppm by 2100 that could result in a decrease of ~0.4 pH units.
Under a worst-case scenario of continued and unabated usage of known fossil fuel
reserves, modeling indicates that average surface ocean pH could fall by a maxi-
mum of 0.77 pH units by 2300 (Caldeira and Wickett 2003 ). Marine organisms
would then experience the lowest pH level for ~20 million years and the most rapid
rate of decline in pH ever (Turley 2008 ). While the OA event experienced 55
million years ago during the Paleocene-Eocene thermal maximum probably
occurred over several thousand years, the present-day anthropogenically induced
event is happening over decades to centuries (Zachos et al. 2005 ).
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