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Alkalinity, carbonate & bicarbonate

The bicarbonate component in seawater is referred to as a gas, the reason for this is that bicarbonate is in a state of equilibrium with carbonates and carbon dioxide in solution. The relative proportion of each component is a function of the pH of the water and the degree of air stripping of carbon dioxide.

The pH of seawater ranges from pH 8.0 to 8.3. In a recycle system the nitrifying bacteria are consuming inorganic carbon which has the effect of reducing the pH. The relationships are quite complex, but it is an important aspect of the system water quality maintenance. I have therefore gone into considerable detail with this section of the report.

Alkalinity buffering equation

1. H20 + CO2      <=>     H2CO3  <=>        HCO3 + H+   <=>       CO3 + 2H+

Nitrification equations

2. NH4+ + 1.5O2     =>     2H+ + 2H2O + NO2-

3. NO2- + 0.5O2    =>      NO3-

4. NH4+ + 1.83 O2 + 1.98 HCO3-   =>       0.021 C5H702N + 0.98 NO3- + 1.041 H2O + 1.88 H2CO3-

5. NH4+ + 1.9O2 + 2HCO3-    =>      1.9 CO2 + 2.9 H2O + 0.1 CH2

From the above equations it can be calculated that for every gram of ammonium oxidised to nitrate, the following occurs;

4.18 grams of oxygen are consumed
7.14 grams of alkalinity as calcium carbonate (as CaCO3) is consumed

or

12 grams of alkalinity as sodium bicarbonate NaHCO3) is consumed

or

4 grams of sodium hydroxide
8.59 grams of carbonic acid is produced (H2CO3)
0.17 grams of cells are produced.

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In a recycle system carbon dioxide (carbonic acid) is being produced by the fish. The nitrifying bacteria also produce acid, and inorganic carbon consumed by the bacteria is converted into cell biomass. This has the net effect of depressing the pH of the water and reducing the alkalinity. Eventually all of the alkalinity in the system will be consumed, the pH will become unstable, and the water will become acidic. This can develop into a serious situation resulting in fish moralities.

Carbon dioxide is in state of equilibrium with carbonates (dependent on pH) and with the atmosphere (dependent on the degree of gas stripping). If there is no aeration in the system then sodium hydroxide may be used to lower the carbon dioxide level and maintain the pH. However this is a rather dangerous solution to the problem since it will be difficult to maintain stable conditions, and there is the risk of over-shoot. In the recycle system there will be aeration and gas stripping as the water splashes around the system and through the biofilters. There will therefore be a net loss of carbonates from the water, thus, additional carbonates must be added. The MagPhlow (MgOH) media in the pressure filters will dissolve into the water in direct response the pH. The MagPhlow is insoluble in the water above a pH of approximately 8.3, this is therefore a much safer approach than the addition of sodium hydroxide.

Sodium bicarbonate can be added to the system to make up for the alkalinity consumed by the biofilter. The ammonium production by the system is approximately 40 kg/day this means that 480 kg (12 x 40) of sodium bicarbonate will be consumed each day. The balance is fairly complex, but it is anticipated that somewhere in the region of 300 kg to 480kg of sodium bicarbonate will need to be added to the system each day.

Strong aeration of the water or gas stripping of carbon dioxide will help to maintain the stability of the water, in turn it will necessitate the addition of sodium bicarbonate at a level close to the upper limit stated above. Strong aeration may also cause problems associate with water temperature regulation, I therefore propose the following for pH and alkalinity regulation;

Only a relatively small amount of sodium hydroxide will be used to provide the fine-tuning of the system. The sodium hydroxide will be in solution and a metering pump that has a maximum capacity to add in the order of 2 litres per hour could be used. The caustic must not be allowed to siphon into the system. This arrangement should work and it provides a compromise that will be safe for the fish