THE EFFECT OF PARTICULATE ORGANIC CARBON AND PARTICULATE

INORGANIC CARBON FORMATION AND DEGRADATION ON THE pH,

CARBONATE ALKALINITY, AND CO2 OF SEAWATER
Temporal and geographic variations in C.A. and CO2 are largely controlled by the
formation and degradation of planktonic POC and PIC. CO2 is supplied to
seawater during the remineralization of planktonic POC and dissolution of PIC.
Formation of biomass and calcareous hard parts requires the removal of CO2.
Thus, vertical profiles of CO2 exhibit vertical segregation characteristic of
biolimiting elements with low concentrations in the surface waters and high
concentrations at depth (Figure 10.2). The formation and degradation of
planktonic POC and PIC influence pH and C.A. as follows. The remineralization of
POC produces CO2, which is rapidly hydrolyzed to carbonic acid, bicarbonate, and
carbonate via the reactions given in Eqs. 5.53 through 5.57. Carbonic acid and
bicarbonate are both weak acids, so their dissociation generates H +. This acid
enhances the dissolution of PIC through the following reaction:
CO2 (aq) + CaCO3(s) + H2O(l) Ca2+(aq) + 2HCO3- (aq)
(15.15)
in which carbonate alkalinity is produced. As illustrated in Eq. 15.3, the formation
of planktonic PIC reduces the alkalinity and CO2 of seawater.
In the case where POC is remineralized in the absence of PIC, the C.A. does not
change because the hydrolysis of CO2 produces one unit of positive charge (H +)
for each unit of negative charge (HCO 3-). Likewise the formation of planktonic
POC reduces the CO2 of seawater but has no effect on C.A.
Over time scales of thousands of years, the carbonate-bicarbonate equilibria
(Eqs. 5.53 through 5.59) maintain the pH of oxic seawater within a narrow range,
i.e., 7.4 to 8.2. Geographic and temporal variations in pH are largely a
consequence of CO2 removal by photosynthesis and CO 2 supply by POC
remineralization. For example, the pH of seawater in the euphotic zone
undergoes a diurnal cycle in which CO 2 uptake by phytoplankton causes an
increase in pH during the day. At night, photosynthesis stops, while dark
respiration continues, leading to release of CO 2 and an ensuing decline in pH. At
depths immediately below the euphotic zone, remineralization of sinking POC
releases acid in quantities that exceed the buffering capacity of the water,
leading to lowered pHs.
15.4.1 Vertical Segregation of CO2 and Alkalinity
CO2 and alkalinity exhibit vertical segregation similar to that of nitrate and
phosphate. An example from the North Pacific is provided in Figure 15.9.
Concentrations of CO2 and alkalinity are low in surface waters because of
uptake of DIC by phytoplankton, some of which is converted to POC and some to
PIC. The biogenic detritus that sinks out of the surface waters is remineralized in
the deep zone, causing CO2 and alkalinity to increase with depth. Because of

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.

Acid is generated via:

CO2(aq) + H2O(l) H+(aq) + HCO3- (aq)

(15.16)

which then reacts with CO23- :

H+(aq) + CO23- (aq) HCO3- (aq)

(15.17)

The net combined stoichiometry of these two reactions is:

CO2(aq) + CO23- (aq) + H2O(l) HCO3- (aq)

(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.