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density stratification, the resolubilized DIC and alkalinity are trapped below the
thermocline.
The increase in CO2 within the thermocline is accompanied by a decrease in pH
caused by the hydrolysis of CO 2 produced by the remineralization of POC. This
supply is so large that significant amounts of CO 2 and H2CO3 are present at
these depths. The [CO32-] reaches minimum values in the depths over which POC
remineralization is most intense because the organic carbon is transformed into
CO2 that reacts with H2O.
(15.16)
(15.17)
(15.18)
Thus, [HCO3-], rather than [CO23-], increases with increasing depth. The
concomitant increase in alkalinity with depth indicates that some PIC has also
dissolved via the chemical reaction depicted in Eq. 15.18.
In Figure 15.9f, the CO2 concentration in the deep zone is seen to be less than
that in the thermocline. This suggests that the waters in the deep zone have
accumulated a smaller amount of the products of biogenic particle
decomposition than have the waters in the overlying thermocline. The cause for
this is twofold: (1) a smaller flux of biogenic particles reaches the deeper depths
as most is remineralized in the overlying waters and (2) thewater in the deep
zone is younger than thewater in the thermocline, having more recently been
at the sea surface as a consequence of meridional overturning circulation. Since
less remineralized CO2 has been added to the waters of the deep zone, the ratio
of [CO23-] to [HCO3-] is higher here than in the thermocline. Eq.15.18 is shifted in
favor of the reactants. Nevertheless, seawater becomes increasingly more
undersaturated withrespect to biogenic calcium carbonate with increasing depth
due to the very large effect of pressure on the Ksp of calcite and aragonite.
Horizontal Segregation of CO2 and Alkalinity
As illustrated in Figure 15.10, both CO2 and T.A. exhibit horizontal segregation
similar to that of nitrate and phosphate. As a water mass moves along the
pathway of meridional overturning circulation, it accumulates biogenic particles.
As the particles remineralize, CO2 and T.A is released into the water mass. Thus,
the deep waters with the highest T.A. and CO2 are the oldest, i.e., those in the
North Pacific ocean.
As a water mass ages, the ratio of [CO 23-] to [HCO3-] declines because the
continuing generation of CO 2 from the remineralization of POC pushes the
equilibrium reaction in Eq. 15.18 further toward the products. Thus, as a deep
water mass ages, it becomes increasingly more undersaturated with respect to
biogenic calcium carbonate.
In the surface waters, geographic variability in CO2 and T.A. are caused by the
effects of temperature on CO2 solubility and by variations in the local rates of
photosynthesis and biogenic calcification. In general, surface water CO2
concentrations are lowest in warm surface waters due to the low solubility of CO 2
at higher temperatures. The lower influx of CO 2 also causes warm surface waters
to have a higher carbonate ion concentration as compared to cold surface
waters. Carbonate ion concentrations are also higher in warm waters because
the Ka for bicarbonate increases with increasing temperature.