Bolus dosing

[GARRIGA]

After 49 pages. Are we ready to just admit we like controversy or was their valid merit to this method labeled literally “one single dose” which is rather ambiguous considering many have been Bolus dosing carbon as well as other additives although some were weekly and most not in the evening. Peroxide closes as that’s in the evening to reduce affect of light degrading it faster although not sure that’s a bad thing since degradation how it works

 

[Lasse]

From FM:s own description of the buffert system. My bold.

This occurs due to the pH rising and the equilibrium converting carbonic acid back to bicarbonate, if this rate of conversion matches the rate of consumption of bicarbonate and carbonate then the alkalinity remains completely fl at even though no alkalinity is being dosed.

The question is - have I been totally wrong - both in my education and experiences for 50 years. They says here that the bicarbonate buffer system goes to the right when photosynthesis consume CO2. I have always thought and been learned that it goes to the left if CO2 will be uptake by photosynthesis (or aerated out in the air) and that total alkalinity will remain stable regardless of pH-dependent amount of CO2 in the water

If CO2 is consumed or vented out in this equation, some H2CO3 goes over to CO2 +H2O. (first double-directional arrow goes to the left) But then the equilibrium between H2CO3 and HCO3 is first disturbed (second double-directional arrow), which means that HCO3 takes up an H ion and forms new H2CO3. The arrow goes to the left. To restore the equilibrium between HCO3 and CO3 (third double-headed arrow), an additional hydrogen ion is taken up to form new HCO3. The arrow goes to the left) The pH rises and the equilibrium between all four becomes a new equilibrium based on the new pH.

I have also been learned that if CO2 rise in the water (if you bubble in it or the CO2 in the air rise) - the equation goes to the right. Excess CO2 (in relation to the prevailing pH) will take up water and form H2CO3 (first bidirectional arrow goes to the right) - again the equilibrium between H2CO3 and HCO3 is disturbed (under the prevailing pH) and some H2CO3 goes over to HCO3 + H. A hydrogen ion is thus released and the pH will be set for the new equilibrium. Second double-directional arrow goes to the right. It will drop. Also the third bidirectional arrow - the equilibrium between HCO3 and CO3 - goes to the right with one more hydrogen ion in solution - further pH lowering and a new equilibrium. During both of these processes, the amount of total alkalinity will not change - IMO - just be redistributed

@Randy Holmes-Farley - correct me if I´m wrong - I´m not a chemist but I think I understand water chemistry rather well.

Sincerely Lasse

 

[Randy Holmes-Farley]

Perhaps the person responsible for changing the labels and calculator was off sick when the formulation was changed, COVID or something, lol.

It happens. Let me give a real analogy.

When my first pharmaceutical polymer was in the very earliest stages of development and scale up, a large batch was being made at a contract manufacturer. Someone at that manufacturer made some sort of error that resulted in one of the ingredients not being added in the specified amount.

The error was significant in the sense that it changed some aspects of the polymer, including the description of it.

By the time it was discovered, the cost and time to remake it was more than the cost to simply verify that it was functionally acceptable and thereafter, the product always had the new composition.

 

[Randy Holmes-Farley]

From FM:s own description of the buffert system. My bold.


The question is - have I been totally wrong - both in my education and experiences for 50 years. They says here that the bicarbonate buffer system goes to the right when photosynthesis consume CO2. I have always thought and been learned that it goes to the left if CO2 will be uptake by photosynthesis (or aerated out in the air) and that total alkalinity will remain stable regardless of pH-dependent amount of CO2 in the water

If CO2 is consumed or vented out in this equation, some H2CO3 goes over to CO2 +H2O. (first double-directional arrow goes to the left) But then the equilibrium between H2CO3 and HCO3 is first disturbed (second double-directional arrow), which means that HCO3 takes up an H ion and forms new H2CO3. The arrow goes to the left. To restore the equilibrium between HCO3 and CO3 (third double-headed arrow), an additional hydrogen ion is taken up to form new HCO3. The arrow goes to the left) The pH rises and the equilibrium between all four becomes a new equilibrium based on the new pH.

I have also been learned that if CO2 rise in the water (if you bubble in it or the CO2 in the air rise) - the equation goes to the right. Excess CO2 (in relation to the prevailing pH) will take up water and form H2CO3 (first bidirectional arrow goes to the right) - again the equilibrium between H2CO3 and HCO3 is disturbed (under the prevailing pH) and some H2CO3 goes over to HCO3 + H. A hydrogen ion is thus released and the pH will be set for the new equilibrium. Second double-directional arrow goes to the right. It will drop. Also the third bidirectional arrow - the equilibrium between HCO3 and CO3 - goes to the right with one more hydrogen ion in solution - further pH lowering and a new equilibrium. During both of these processes, the amount of total alkalinity will not change - IMO - just be redistributed

@Randy Holmes-Farley - correct me if I´m wrong - I´m not a chemist but I think I understand water chemistry rather well.

Sincerely Lasse

You are not wrong (though I would put 2H+ in the far right to make that part more clear)

 

[mfollen]

I'm not trying to speak on behalf of Fauna Marin, but I am very curious of the claims of the Kalkwasser long-term impact on our systems. Thanks to everyone diving in to this.

I summarized some of the takeaways that was covered during last night's Reefbum live stream (thank you to Keith, Claude, and Mike for making that happen!) regarding this effect.
Perhaps this summary can help add some fuel to the great research and discussions in this thread.
Again, this is not from Fauna, but it is one audience member's takeaway of what was discussed during a live stream. I may be incorrect in the below summary regarding what was intended to be stated or to be taken away by the audience.

The broken buffer system refers to a situation where long-term dosing of carbonates or kalkwasser in a reef tank leads to excessive precipitation throughout a reef system. This precipitation may bind minerals, potentially amino acids or other organics to the rocks and surfaces in a system.
This precipitation causes a cycle where bacteria break down these precipitates, producing organic acids and these organic acids making H+ that lower pH levels. To counteract this pH drop, continual dosing of high pH solutions becomes necessary, leading to a dependency on dosing and potentially unstable pH levels if dosing is interrupted.

Transitioning from carbonate-based dosing to other methods, like the bolus method, can initially decline and destabilize alkalinity levels where your buffer system is no longer active which may occur for several days before stabilizing again with the bolus method.
So the broken buffer system is a name used to describe when the bolus method needs a longer time to stabilize the alkalinity again.
Ultimately, using bicarbonate-based systems can minimize precipitation and maintain tank stability over the long term without excessive dosing requirements.

 

[BeanAnimal]

I'm not trying to speak on behalf of Fauna Marin, but I am very curious of the claims of the Kalkwasser long-term impact on our systems. Thanks to everyone diving in to this.

I summarized some of the takeaways that was covered during last night's Reefbum live stream (thank you to Keith, Claude, and Mike for making that happen!) regarding this effect.
Perhaps this summary can help add some fuel to the great research and discussions in this thread.
Again, this is not from Fauna, but it is one audience member's takeaway of what was discussed during a live stream. I may be incorrect in the below summary regarding what was intended to be stated or to be taken away by the audience.

The broken buffer system refers to a situation where long-term dosing of carbonates or kalkwasser in a reef tank leads to excessive precipitation throughout a reef system. This precipitation may bind minerals, potentially amino acids or other organics to the rocks and surfaces in a system.
This precipitation causes a cycle where bacteria break down these precipitates, producing organic acids and these organic acids making H+ that lower pH levels. To counteract this pH drop, continual dosing of high pH solutions becomes necessary, leading to a dependency on dosing and potentially unstable pH levels if dosing is interrupted.

Transitioning from carbonate-based dosing to other methods, like the bolus method, can initially decline and destabilize alkalinity levels where your buffer system is no longer active which may occur for several days before stabilizing again with the bolus method.
So the broken buffer system is a name used to describe when the bolus method needs a longer time to stabilize the alkalinity again.
Ultimately, using bicarbonate-based systems can minimize precipitation and maintain tank stability over the long term without excessive dosing requirements.

Sounds like dithering after being called out as the hole gets deeper. When spurious "science" is questioned, the best thing to do is add on more "science" that can't be verified to explain the "science" that couldn't be verified...


I have nothing (at all) against Mike or Keith - but It certainly appears that Claude is making the talk show rounds in an attempt to change the narrative and give credibility to all of this after being caught like a deer in headlights. Just may take worth what you paid for it.

 

[mfollen]

I haven’t paid for anything. Just open to learn and hear from the community

 

[Lasse]

long-term dosing of carbonates or kalkwasser

FYI - Theses two methods rise pH in to different ways. Carbonates by breaking the equilibrium in the carbonate buffering system and force a conversion of the excess carbonate ions to bicarbonate ions. Carbonate ion = CO3 and bicarbonate ion = HCO3. The system takes up hydrogen ions and therefore the pH is raised until the new equilibrium between HCO3 and CO3 is reached.

Limewater works in such a way that Hydroxide ions are added to the aquarium water. The pH is raised directly and the equilibrium between bicarbonate and carbonate is disturbed here as well - but in this case some bicarbonate is forced over to become carbonate - that is, releasing hydrogen ions so that the pH increase is slowed down. This is the buffering effect. Anyone can test this by taking RO water. Measure the pH with a pH probe and see what happens when hydroxide is dropped into the solution. Not much is needed before the pH is 14. Raise the alkalinity of the water to 7 dKH (you can use bicarbonate for this and the pH stays at about 8.2) Add hydroxide ions again and you will see that significantly more hydroxide ions are needed to drive the pH up to 14.

Sincerely Lasse

 

[KGV]

If anything, after 50 pages, we all became better chemists.

 

[Randy Holmes-Farley]

I agree that it is trying to reset the claim after many clearly false statements.

We can all debate the merits of bicarbonate vs carbonate vs hydroxide, and perhaps independently, the merits of any particular pH range, without making false statements.

That said, the take away described above is not convincing to me at all as an explanation of old tank syndrome (whether it is a real thing or not).

I agree that higher pH, and also possibly dosing of higher pH additives even without the average pH rising may lead to more abiotic precipitation of calcium carbonate. And that deposit will attract organics, phosphate, and magnesium.

But here’s where I think it goes off the rails. The claim stated above is that later consumption of the bound organics lowers pH, requiring more and more high ph additives to offset it. I’m not convinced these organics are biologically available, but assuming they are, how is their metabolism reducing pH any more likely than if those same organics were just still just floating around in the water waiting to be metabolized. It almost seems turned backwards, with more metabolism and pH lowering likely when they do not bind.

Second, I had not actually heard claims that old tank syndrome was a pH effect at all. I guess it depends on what one is talking about. My tank after 20 years of dosing kalkwasser did not run at noticeably lower pH than previously. The only times I noted a significant change was when the skimmer was offline (pH rose) and when we got new storm windows (pH declined).

Third, there are a lot of people who have been dosing fine particle calcium carbonate for quite a long time as coral snow. SunnyX has been doing it a long time, claims it works great, and has a long thread about it.

Extreme Water Clarity and Cyano Eradication, Made Easy!

Edit 10/092023: Note that I have tweaked the formula a bit. You can find an updated video here: Coral Snow Link: Coral Snow Hello all! I have been reefing now for about 25 years, and over those many years I have picked up many tips, tricks, and best habits/practices. From a hobbyist and...

www.reef2reef.com

Perhaps FM should make it clear to him that his tank is going to die an early death of old tank syndrome from all that calcium carbonate.

 

[Tavero]

I am shocked that a company puts out such utterly and grossly incorrect ideas. They need to send someone at the company to study chemistry before spouting nonsense.

I’m on a phone now and it’s hard to write long passages, but surely such misleading info deserves a long and detailed response.

It's kinda sad TM is trying to sell more and more snake oil in the last few years. They were a very respectable company before. I don't know what happened?

Edit: I've seen now that thread started in may. I hope I didn't desecrate it by doing necromancy

 

[BeanAnimal]

But here’s where I think it goes off the rails. The claim stated above is that later consumption of the bound organics lowers pH, requiring more and more high ph additives to offset it. I’m not convinced these organics are biologically available, but assuming they are, how is their metabolism reducing pH any more likely than if those same organics were just still just floating around in the water waiting to be metabolized. It almost seems turns backwards, with more metabolism and pH lowering likely when they do not bind.

And that is also assuming that this evil precipitate is all somehow collected and available in the system and not exported by any means. Last I checked my 20+ year old reef's sand did not turn solid and my rocks have not grown, nor do I have new precipitate stalagmites... I mean I haven't seen those since I was a kid

Second, I had not actually heard claims that old tank syndrome was a pH effect at all. I guess it depends on what one is talking about.

Mike takes credit for the term (way back in the 90's)... and it was always used in reference to bound phosphate buildup reaching a tipping point and then being released by various mechanisms.... buy it or not.

Claude has simply dithered his "science" to add pH to the theory proposed by Mike. Thus the podcast, Marketing is a science too

 

[Randy Holmes-Farley]

And that is also assuming that this evil precipitate is all somehow collected and available in the system and not exported by any means. Last I checked my 20+ year old reef's sand did not turn solid and my rocks have not grown, nor do I have new precipitate stalagmites... I mean I haven't seen those since I was a kid

I think I had those too!

Like stalagmites, I think a lot of precipitate just builds on top of old precipitate or sand or rock or whatever. It is not necessarily generating lots of new little lose particles, but buildup like we see on pump impellers. Anything buried is mostly lost from microbial action.

 

[twentyleagues]

I agree that it is trying to reset the claim after many clearly false statements.

We can all debate the merits of bicarbonate vs carbonate vs hydroxide, and perhaps independently, the merits of any particular pH range, without making false statements.

That said, the take away described above is not convincing to me at all as an explanation of old tank syndrome (whether it is a real thing or not).

I agree that higher pH, and also possibly dosing of higher pH additives even without the average pH rising may lead to more abiotic precipitation of calcium carbonate. And that deposit will attract organics, phosphate, and magnesium.

But here’s where I think it goes off the rails. The claim stated above is that later consumption of the bound organics lowers pH, requiring more and more high ph additives to offset it. I’m not convinced these organics are biologically available, but assuming they are, how is their metabolism reducing pH any more likely than if those same organics were just still just floating around in the water waiting to be metabolized. It almost seems turned backwards, with more metabolism and pH lowering likely when they do not bind.

Second, I had not actually heard claims that old tank syndrome was a pH effect at all. I guess it depends on what one is talking about. My tank after 20 years of dosing kalkwasser did not run at noticeably lower pH than previously. The only times I noted a significant change was when the skimmer was offline (pH rose) and when we got new storm windows (pH declined).

Third, there are a lot of people who have been dosing fine particle calcium carbonate for quite a long time as coral snow. SunnyX has been doing it a long time, claims it works great, and has a long thread about it.

Extreme Water Clarity and Cyano Eradication, Made Easy!

Edit 10/092023: Note that I have tweaked the formula a bit. You can find an updated video here: Coral Snow Link: Coral Snow Hello all! I have been reefing now for about 25 years, and over those many years I have picked up many tips, tricks, and best habits/practices. From a hobbyist and...

www.reef2reef.com

Perhaps FM should make it clear to him that his tank is going to die an early death of old tank syndrome from all that calcium carbonate.

OH No! I have been doing the evil coral snow since April is my tank doomed? How long do I have? Should I say my farewells tonight? lol

 

[Randy Holmes-Farley]

OH No! I have been doing the evil coral snow since April is my tank doomed? How long do I have? Should I say my farewells tonight? lol

Weeks at most. Maybe only days...Better get your affairs in order now.

 

[twentyleagues]

Weeks at most. Maybe only days...Better get your affairs in order now.

RIP tank RIP...... the good ones always go young.

 

[areefer01]

It's kinda sad TM is trying to sell more and more snake oil in the last few years. They were a very respectable company before. I don't know what happened?

I understand that the T and the F is in close proximity to one another albeit on another row but this has nothing to do with TM.

TM - usually references or is short for Tropic Marin
FM - Fauna Marin - is what this thread is about and their Bolus method

 

[carbl]

I don't know what it's like in the USA, but here in Germany many people are giving up the hobby. Energy prices are pretty high, plus inflation, high rents and house prices.
On the other hand, there are more and more manufacturers and most of the supply systems are carbonate based, like Oceamo, ATI and others. Or things like all for reef.
Balling light is 20 years old and mainly based on bicarbonate, basically cheap baking soda.
All these explanations and claims by FM have become stories for me. Stories that are intended to unsettle people (old tank syndrome) while at the same time throwing around important-sounding terms such as peptides, polymers, etc.
It is relatively clear to me that the aim is to protect and improve one's own market position.

Claude doesn't think much of lime water as a main supply either and criticizes it in some videos. Sure, lime water is also cheap, a competitor to his supply and lately there are more and more people who like it and want to try it out.
All this will cost market share. Then you just tell stories about why your own product is superior to others.

 

[Lasse]

My bold

This precipitation may bind minerals, potentially amino acids or other organics to the rocks and surfaces in a system.
This precipitation causes a cycle where bacteria break down these precipitates, producing organic acids and these organic acids making H+ that lower pH levels.

"may" - I would love to see any pathways for this. That excess calcium can bind phosphate into calcium phosphate is well known and in use in many wastewater treatments plant around the world but that the main precipitation of calcium carbonate (limestone) would give the bacteria organic food that not already exist in the aquarium (organic detritus) - I do not understand. To state that i may be organic acids that lower the pH in a system with a bicarbonate buffringssystem (alkalinity) that always - in different ways - is uphold by the aquarist is way ahead of my pay grade. Its impossible because the buffer system take care of it if we just withhold a certain level.

What cause pH problems in our aquariums? Its clear for me that as long as we have the alkalinity (the buffer system) in a steady level - pH is only depended of the CO2 gas concentration in the water.

What determines that level then? The air's CO2 concentration and the equilibrium between CO2 in air and water is one such factor. However, in a closed system like an aquarium - IMO - cellular respiration is the most important factor. All living things absorb carbon for their own biomass. Autotrophic organisms - plants, algae some bacteria and other organisms that use light as well as the chemoautotrophic organisms (such as nitrifying bacteria) absorb inorganic carbon as carbon dioxide. Heterotrophic organisms like us, other animals, most bacteria and other organisms use organic carbon bound in the food we eat.

Warm-blooded animals only use about 10% of the food (including the organic carbon) as biomass - the rest goes away as waste - as for organic carbon, its "waste" is carbon dioxide (CO2). Cold-blooded animals such as fish and bacteria (and other "cold blooded animals") are a bit more efficient - between 20 - 25% become biomass. But that means about 75% becomes waste. This means that of the organic carbon we add as food or in various methods for adding DOC (dissolved organic carbon) - 75% ends up as CO2 in the water.

If this produced excess of CO2 is not vented out of the aquarium (if the CO2 content in the surrounding air is low enough) or is not taken up by photosynthesis it will accumulate in the water and result in very low pH but the alkalinity can still be good. The best example of this is long transports of fish in plastic bags. I have measured pH levels below 6.4 in such water after 48 hours of transport. However, the alkalinity is still good. If you open the bag - take the fish out just in case - aerate the water, the pH will rise to the level corresponding to the current CO2 equilibrium between water and ambient air.

Sincerely Lasse

 

[Tavero]

I understand that the T and the F is in close proximity to one another albeit on another row but this has nothing to do with TM.

TM - usually references or is short for Tropic Marin
FM - Fauna Marin - is what this thread is about and their Bolus method

Thanks for the reminder. I'm always mixing up these companies because their names are so similar. In that case both of them seem to release methods/products with questionable results and sources by now.