Distribution of DIC (Carbonate) species with pH for 25C and 5,000 ppm salinity (e.g. salt-water swimming pool) - Bjerrum plot
misleading Bjerrum plot for carbonate species in a closed system

An interesting and widely misunderstood concept is the distribution of carbonate species (DIC:  dissolved inorganic carbon) in an aquarium.  What you usually see is a form of Bjerrum plot where it looks very much like the amount of dissolved CO2 goes to zero as the pH gets much higher than 7.  Where this goes wrong is that whilst the plot successfully illustrates the relative fraction of DIC species with respect to each other, what it misses is that in an open system (exposed to atmosphere) the total amount DIC is not constant with respect to pH.

Note that in this graph (and most others as well) the species listed as H2CO3 (nominally carbonic acid), is actually composite carbonic acid:  an equilibrium of about 99.7% dissoved CO2 and 0.3% carbonic acid.  The equilibrium between dissolved CO2 and carbonic acid is independent of pH. 

High pH converts carbonic acid to other forms of carbonate

Carbonic acid can be deprotonated under high pH conditions, converting first to bicarbonate, and subsequently to carbonate if the pH gets high enough.  This process is conveyed by the Bjerrum plot, shown above for closed systems.

Total DIC increases exponentially above pH 5.5

total dissolved inorganic carbon wrt pH
DIC forms vs. pH

There is an essentially infinite supply of CO2 in the atmosphere, so an aquarium that doesn’t have some active process modifying CO2 levels will, within hours, reach an equilibrium between dissolved CO2 in the water and CO2 in the atmosphere.  The relative amounts of these are described by Henry’s law and will come out to something between 1 and 3 ppm (parts per million) CO2 dissolved in the water, compared to indoor atmospheric CO2 gas which is generally between 400 and 1000 ppm.  This equilibrium between dissolved and atmospheric CO2 is pH independent – the horizontal green line in the ‘DIC forms vs. pH‘ figure below – it is always a constant amount. 

Above 5.5 the carbonic acid starts being converted to other forms of carbonate species (see the Bjerrum plot), but you never run out of carbonic acid when this happens because carbonic acid can always be replenished from atmospheric CO2 (again, Henry’s law).  This means the bicarbonate and carbonate forms of dissolved inorganic carbon have no upper limit to how much can accumulate – how much accumulates and in which form is entirely driven by pH; these are the blue and orange lines in the ‘DIC forms vs. pH’ picture.  The total amount of all carbonate species shown by the light blue curve grows exponentially with increasing pH (note that the Y-axis is log10 transformed).  The high-pH driven accumulation of carbonate forms collectively is the major component of aquarium alkalinity.

The Bjerrum plot is still correct

So what does it mean when from the Bjerrum plot at high pH it looks like the levels of dissolved CO2 go to zero?  The key is that the Bjerrum plot shows relative percentages and not absolute amounts.  The percentage of dissolved CO2 doesn’t actually go all the way to zero, it just becomes very small relative to the total of all DIC, which is entirely consistent with the exponential increase in total DIC at high pH.  It is not that the levels of dissolved CO2 become small with increasing pH, those stay constant, instead it is the amount of the other carbonate forms of DIC that become very large.

Changing aquarium pH does not change dissolved CO2

What that all means is that if you want better aquatic plant growth and you want to make that happen by increasing the amount of dissolved CO2 available to the plants, you can’t accomplish that by maintaining a stable low aquarium pH.  You might have other reasons to prefer your water have a lower pH, but dissolved CO2 levels won’t be affected.  If you want to reliably increased dissolved CO2 in the water, your best way is to inject pure CO2 gas directly into the water.  Injecting pure CO2 gas is a non-equilibrium method; once you stop injecting CO2 gas into the water, levels of dissolved CO2 will gradually fall to those determined by Henry’s law.  Injecting CO2 gas into the water will (temporarily) decrease the pH of the water, but that pH decrease is a consequence of increasing dissolved CO2, rather than being the cause of an increase in dissolved CO2.

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