alk. consumption to decrease with carbon dosing?

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It’s been a while since I carbon dose, but is it normal for alk. Consumption to decrease when carbon dosing? I’ve been dosing nopox 1-2ml total for 90g system for the last 2wks. I’ve noticed my alk is slowly climbing.

My no3 is somewhere between 5-10ppm and po4 0 ppb. Along with feeding more and carbon dosing to drop my nitrates a bit, I was hoping po4 would climb?
 
Decline of nitrate by 50 ppm will boost alkalinity by about 2.3 dKH, so that may be what you are observing, not a demand decline.

But carbon dosing may also lower pH, and that will reduce demand, by corals or abiotic precipitation or both. [emoji3]
 
Decline of nitrate by 50 ppm will boost alkalinity by about 2.3 dKH, so that may be what you are observing, not a demand decline.

But carbon dosing may also lower pH, and that will reduce demand, by corals or abiotic precipitation or both. [emoji3]
I didn't realize nitrates were so directly linked to alkalinity. What is the relationship of those two, Randy?
 
I didn't realize nitrates were so directly linked to alkalinity. What is the relationship of those two, Randy?

Having nitrate has no impact on alkalintiy. It is the production (reduces alk) and consumption (adds alk) that has an impact. if nitrate is steady, those two exactly offset. If there's an imbalance so nitrate is rising or falling, then alk would be falling or rising, respectively.

Here's a discussion of why:

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. (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:


  1. (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:


  1. (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 levels.
 
Having nitrate has no impact on alkalintiy. It is the production (reduces alk) and consumption (adds alk) that has an impact. if nitrate is steady, those two exactly offset. If there's an imbalance so nitrate is rising or falling, then alk would be falling or rising, respectively.

Here's a discussion of why:

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. (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:


  1. (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:


  1. (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 levels.
Awesome! This is great to know! Great write up and explanation as always!
 
Decline of nitrate by 50 ppm will boost alkalinity by about 2.3 dKH, so that may be what you are observing, not a demand decline.

But carbon dosing may also lower pH, and that will reduce demand, by corals or abiotic precipitation or both. [emoji3]

I noticed my ph dropped to 7.9 at the lowest, it’s not dropped under 8 in months.
 
Decline of nitrate by 50 ppm will boost alkalinity by about 2.3 dKH, so that may be what you are observing, not a demand decline.

But carbon dosing may also lower pH, and that will reduce demand, by corals or abiotic precipitation or both. [emoji3]

^This, plus any changes can also slow growth temporarily as the corals acclimate to the new environment.
 
Hey Randy,

Digging up this old thread because it’s really well written and this might help me and others solve a problem.

I was cleaning a power head, and an unknown amount of household vinegar spilled into the back of my JBJ Nano Cube 28 gallon. I was cleaning a power head and I turned it on and it sprayed into the tank. It fell into the back of the “sump” area dropping my pH from 8.2 to 6.5 according to the pH probe. The volume is appx 4 liters. The water circulation from the return was off. I immediately did a water change, about 1 gallon and daily since since. The pH was only brought back up to 7.8 when I decided to turn it back on.

pH has been sluggish, with no dinurnal high swing, but falls very low into 7.75 into the early morning day hours. Despite getting up to regularly 8.4 in the day time with kalkwasser before the vinegar spill. For three days I struggle to get over 8.01!!!!

Is this because there’s too much carbon in my system, producing too much H+ through biological processes? PH doesn’t change with windows open or aeration.

Could I drive consumption of excess carbon with the addition of Nitrates? My levels are 0. So in theory could this drive bacteria growth since Nitrogen is limited?
 
I suspect the acetate and any direct pH effect from the vinegar is gone by now, but can you post the current values for alkalinity, nitrate and phosphate?

Just on the nitrate theory, if there is acetate remaining whose metabolism is producing Co2 and lowering ph, then there is enough nitrate for that to happen. If it is nitrate limited, and acetate remains, then the pH would not presently be depressed (no Co2 is being formed) unless the alkalinity was greatly depleted.

If the pH meter is in the sump, then the low pH may have "cleaned" it a bit, and recalibration may be needed.
 
I suspect the acetate and any direct pH effect from the vinegar is gone by now, but can you post the current values for alkalinity, nitrate and phosphate?

Just on the nitrate theory, if there is acetate remaining whose metabolism is producing Co2 and lowering ph, then there is enough nitrate for that to happen. If it is nitrate limited, and acetate remains, then the pH would not presently be depressed (no Co2 is being formed) unless the alkalinity was greatly depleted.

If the pH meter is in the sump, then the low pH may have "cleaned" it a bit, and recalibration may be needed.

At the time of accident, 6.7 dKH which I keep my alkalinity on the lower side 7.0 to 7.5 +/- 0.05, so I do dip lower or higher, currently sitting at 7.6 dKH. Check via Hanna and Salifert.

Nitrates - 0.0 ppm Salifert
Phosphate 0.0 ppm Hanna


ZeoVit —
Top it off, I am doing ZeoVit for the past 6 weeks — though I stop adding carbon sources when the spill happen. As not to add fuel to the fire. I am using the ZeoLite media, which is said to absorb NH3+. Which is very interesting based on the reaction equations above. The media is keeping my NOlevels very low. Though I don’t want to run this low and using ZeoVit for me isn’t about reaching zero, but pushing zero and controlling nutrients.

pH probe poisoning —
I thought that too. I was surprised quickly that could happen. It going to 6.5 for about an hour could have a significant effect on calibration? I will recalibrate anyways.


I think I am N limited and P limited for the amount of carbon that’s in the system. I have been doing daily 1 gallon water changes since the accident.
 
A pH change would not normally cause a pH meter to need recalibration, but if there was any calcium carbonate on it, it would dissolve at pH 6.5, and that might impact calibration.
 

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