@Randy Holmes-Farley thank you so much - this is all very helpful. I'm finding myself in a similar situation as OP
I've been struggling for a couple months to maintian alk, using saturated kalk + 2 part. I finally tested calcium over the weekend and found we're in 'zone 4' as you described previously in an article
I've since stopped the kalk & I'm dosing just sodium bicarbonate till the calcium comes back down. The numbers are getting back in line
I'm hoping I'll be able to top off lime water again after, because I'm dosing manually right now
As a follow up question, could you elaborate on how those last two factors may throw alk/cal off balance?
Well, first, in your case, limewater will very slowly raise calcium relative to alkalinity since it provides the exact ratio in pure calcium carbonate, but in a reef tank, some magnesium gets into the structure in place of calcium, reducing its demand. That's part of the reason i used a lower calcium mix: normal IO.
I discuss the nitrate effects in detail here:
When Do Calcium and Alkalinity Demand Not Exactly Balance? by Randy Holmes-Farley - Reefkeeping.com
http://reefkeeping.com/issues/2004-12/rhf/index.htm
Alkalinity Decline in the Nitrogen Cycle
One of the best known chemical cycles in aquaria is the nitrogen cycle. In it, ammonia excreted by fish and other organisms is converted into nitrate. This conversion produces acid, H+ (or uses alkalinity depending on how one chooses to look at it), as shown in equation 1:
(1) NH3 + 2O2 --> NO3- + H+ + H2O
For each ammonia molecule converted into nitrate, one hydrogen ion (H+) is produced.
If nitrate is allowed to accumulate to 50 ppm, the addition of this acid will deplete 0.8 meq/L (2.3 dKH) of alkalinity.
However, the news is not all bad. When this nitrate proceeds further along the nitrogen cycle, depleted alkalinity is returned in exactly the amount lost. For example, if the nitrate is allowed to be converted into N2 in a sand bed, one of the products is bicarbonate, as shown in equation 2 (below) for the breakdown of glucose and nitrate under typical anoxic conditions as might happen in a deep sand bed:
(2) 4NO3- + 5/6 C6H12O6 (glucose) + 4H2O --> 2 N2 + 7H2O + 4HCO3- + CO2
In equation 2 we see that exactly one bicarbonate ion is produced for each nitrate ion consumed.
Consequently, the alkalinity gain is 0.8 meq/L (2.3 dKH) for every 50 ppm of nitrate consumed.
Likewise, equation 3 (below) shows the uptake of nitrate and CO2 into macroalgae to form typical organic molecules:
(3) 122 CO2 + 122 H2O + 16 NO3- --> C106H260O106N16 + 138 O2 + 16 HCO3-
Again, one bicarbonate ion is produced for each nitrate ion consumed.
It turns out that as long as the nitrate concentration is stable, regardless of its actual value, there is no ongoing net depletion of alkalinity. Of course, alkalinity was depleted to reach that value, but once it stabilizes, there is no continuing alkalinity depletion because the export processes described above are exactly balancing the depletion from nitrification (the conversion of ammonia to nitrate).
There are, however, circumstances where the alkalinity is lost in the conversion of ammonia to nitrate, and is never returned. The most likely scenario to be important in reef aquaria is when nitrate is removed through water changes. In that case, each water change takes out some nitrate, and if the system produces nitrate to get back to some stable level, the alkalinity again becomes depleted.
If, for example, nitrate averages 50 ppm at each water change, then over the course of a year with 10 water changes of 20% each, the alkalinity will be depleted by 1.6 meq/L (4.5 dKH) over the course of that entire time period.
This process is one of the primary reasons that fish-only aquaria that often export nitrate in water changes need occasional buffer additions to replace that depleted alkalinity.
While the magnitude of the depletion described in the paragraph above is fairly easy to understand, it also can be converted into units that clarify the imbalance. The impact of alkalinity depletion on the calcium and alkalinity demand balance depends, of course, on the amount of calcium and alkalinity added (and consumed) over the course of that same year.
For a typical reef aquarium (assuming a daily addition of saturated limewater equal to 2% of the tank's volume), the amount of alkalinity added during the course of a year is 297.8 meq/L. Likewise, the amount of calcium added is 5,957 ppm Ca++, given the ratio of 1 meq/L of alkalinity for every 20 ppm of calcium that has been discussed above. If that 1.6 meq/L of alkalinity is added to create a larger demand of 299.4 meq/L over the course of a year, the new ratio for the total demand becomes 19.90 ppm Ca++ per 1 meq/L of alkalinity.
Consequently, while this effect of nitrate production on alkalinity is enough to be noticed over the course of a year, it is substantially smaller than the other effects discussed in this article, and is unimportant for aquaria that maintain low nitrate level
