Bolus dosing

[Oldreefer44]

I will be tracking PH 2 or 3 times a day as well as ALK, Ca and Mg and will report in after 30 days. Will also compare to Kalk and AFR that I have been using since AFR came out. Will also compare ICP results especially relative to the few minor trace elements that are always shown to be deficient. There will not be any anecdotal opinions such as "my corals look better" or "my corals are growing faster".

 

[Randy Holmes-Farley]

I will be tracking PH 2 or 3 times a day as well as ALK, Ca and Mg and will report in after 30 days. Will also compare to Kalk and AFR that I have been using since AFR came out. Will also compare ICP results especially relative to the few minor trace elements that are always shown to be deficient. There will not be any anecdotal opinions such as "my corals look better" or "my corals are growing faster".

How are you setting a dose? Are you going to try to match the alk?

 

[Oldreefer44]

Good question. Yes I will have to play with it until i can get it to 8.5 dkh which is where I am at now.

 

[Randy Holmes-Farley]

Good question. Yes I will have to play with it until i can get it to 8.5 dkh which is where I am at now.

Sounds good. Looking forward to it.

 

[Oldreefer44]

Will also send out a "before" ICP to FM to set a baseline.

 

[carbl]

Hearsay is always a problem, so I have translated some key statements literally from the video.

About the missing bicarbonate:
"Part of the carbonate hardness is not available. You add 2kh mathematically, but no 2kh is created. Microcrystalline precipitates are formed, which then form small fractions that are mainly deposited on the surfaces. This happens within several hours and then they go back into re-dissolution over several hours due to the carbonic acid and CO2 activity that the material brings with it.
Very roughly: you then only measure 1kh and over time the rest goes into the re-dissolution phase and provides the alkanity for the next few hours."

About the precipitations of carbonates and hydroxides:
"The problem with precipitation is, and this is often argued, that only magnesium hydroxide is formed. That is one of the typical myths we have.
And it has now been proven by Armin Glaser (German chemist) and countless studies (University of Hawaii etc.) that this is not the case.
We have a production of various carbonates, but these hydroxides, which dissolve again afterwards, also pull organic substances, amino acids and trace elements close to them. So the adsorption capacity is even greater than with carbonates and they often remain in the deposits, even if some of them dissolve again. What is forgotten is the adsorption capacity of these ultra-fine materials."

About the buffer system:
"The buffer system is related to the fact that we have various precipitation mechanisms, not only for the precipitation of chemicals during dosing, which is one thing. Other precipitations also occur on organic surfaces or on ceramic/calcareous surfaces, which practically cling to the surfaces like micro crystals.
They then dissolve again due to the storage of CO2 or carbonic acid.
It is a combination of the addition and the saturation point of the lime. Seawater is not particularly stable. If we increase the pH value or change the carbonate content or the calcium content compared to the balanced average, which is maintained by magnesium, we automatically produce precipitates. No matter what we dose, this has nothing to do with bicarbonate.

With bicarbonates, it's just that the bolus dosage briefly lowers the pH value, i.e. we produce a lot of CO2 and also carbonic acid. And this turns into a certain type of liquid called the dense liquid phase (you can google it). And certain crystalline forms are formed that are stimulated by the particles in the tank and these in turn go back into solution bit by bit in order to reach this saturation point and that is this buffer battery.
At high pH values ( i guess he means when we use hydroxide and carbonates supply systems) , we produce a lot of carbonates. The CO2 is bound there, sinks to the bottom and remains there. It does not dissolve because we maintain a high pH value. Carbonates no longer dissolve at pH 8.4-8.5. Although there is re-dissolution, this happens in the biofilms due to low pH values or the production of organic acids.
It is a misconception that the lime simply precipitates. It takes everything we have in the aquarium with it in terms of organic matter. Dyes, amino acids, food etc. and that's why all the dirt in the sand is black or brown."

Then he switches to the sand discussion.
If I have understood this correctly, it is not primarily about the precipitations when dosing carbonates and hydroxides, but generally about precipitations that no longer dissolve at high pH values (typical for lime water and carbonate dosing).
If, on the other hand, bicarbonate supplies are used, the precipitates are gradually dissolved due to the drop in pH value (i.e. healing of the broken buffer system).
I cannot understand this, perhaps others can.

 

[Garf]

In this new vid from Doug, he said he's adding 1.8 DKH but only getting a recorded 0.4DKH increase / consumption; I'll screenshot the chart;



Green is pH, grey is Alk;

 

[Randy Holmes-Farley]

"Part of the carbonate hardness is not available. You add 2kh mathematically, but no 2kh is created. Microcrystalline precipitates are formed, which then form small fractions that are mainly deposited on the surfaces. This happens within several hours and then they go back into re-dissolution over several hours due to the carbonic acid and CO2 activity that the material brings with it.
Very roughly: you then only measure 1kh and over time the rest goes into the re-dissolution phase and provides the alkanity for the next few hours."

Thanks for the translations.

That is not any sort of viable explanation for why it is not present in a beaker test of the alk in the product. An alkalinity titration takes the pH far lower (pH in the 4's) than is needed to dissolve any tiny calcium carbonate particles, so if they formed they would be counted and is also far lower than is present in the tank at any time of day.

It is certainly possible that such solids form, and they are more likely to form with higher pH additives. They seem to want to claim it is a benefit when using bicarbonate and a detriment that breaks the buffer system when using high pH additives such as carbonate or hydroxide. Which is it?

FWIW, there's no evidence that the pH in tank gets low enough to dissolve calcium carbonate particles. There are local situations where it may happen (deep in sand beds, inside sea cucumber GI tracts, under bacterial biofilms, etc, but calcium carbonate particles simply coating surfaces such as live rock are exposed to water near pH 8, where they are not going to readily dissolve.

About the precipitations of carbonates and hydroxides:
"The problem with precipitation is, and this is often argued, that only magnesium hydroxide is formed. That is one of the typical myths we have.
And it has now been proven by Armin Glaser (German chemist) and countless studies (University of Hawaii etc.) that this is not the case.
We have a production of various carbonates, but these hydroxides, which dissolve again afterwards, also pull organic substances, amino acids and trace elements close to them. So the adsorption capacity is even greater than with carbonates and they often remain in the deposits, even if some of them dissolve again. What is forgotten is the adsorption capacity of these ultra-fine materials."

I'm not going to defend what anyone else has said, but I have said hundreds of times that calcium carbonate may also be formed when dosing high pH additives, which is why you want to mix in high pH additives quickly.

I have also said hundreds of times that calcium carbonate surfaces rapidly bind many things, including organics. That statement is literally part of every repost of my directions of how to stop excessive precipitation of calcium carbonate. I don't know if their assertion about hydroxides remaining intact and not dissolving over time is true or not, but the assertion of their surfaces remaining hydroxide is likely incorrect and obviously is without any supporting data. Exposed hydroxides are likely to rapidly react to form carbonate. Regardless, there is no doubt that precipitated minerals bind things. That is why many people dose calcium carbonate particles (coral snow) to begin with.

"The buffer system is related to the fact that we have various precipitation mechanisms, not only for the precipitation of chemicals during dosing, which is one thing. Other precipitations also occur on organic surfaces or on ceramic/calcareous surfaces, which practically cling to the surfaces like micro crystals.

I certainly agree that is possible in many scenarios. I discuss that with reefers all the time (excessive precipitation scenarios).

They then dissolve again due to the storage of CO2 or carbonic acid.

They may redissolve for various reasons where the local pH may be lower than in the tank water (mentioned above), but I have no idea what he is talking about with stored CO2 or carbonic acid. CO2 and carbonic acid are ONLY a function of tank water ph. There's no hidden CO2 waiting to spring out and do something, unless one is talking about metabolism or organics that produce Co2, such as when organic carbon dosing. Bicarbonate bolus dosing certainly does not store up hidden CO2 or carbonic acid that is not exactly reflected by the pH.

It is a combination of the addition and the saturation point of the lime. Seawater is not particularly stable. If we increase the pH value or change the carbonate content or the calcium content compared to the balanced average, which is maintained by magnesium, we automatically produce precipitates. No matter what we dose, this has nothing to do with bicarbonate.

Seawater at any pH above 7.7 and normal alk (or higher) is supersaturated with calcium carbonate, and it can precipitate. The higher the alkalinity and the higher the pH, the more prone the seawater is to have precipitation. A number of things, not just magnesium, but also including organics and phosphate, serve to slow or stop that precipitation. Certainly in the local area where alkalinity additives (such as bicarbonate) are added, this can happen from high alk and with dosing of high alk and pH supplements such as carbonate and hydroxide, it is even more likely. That, again, is why it is important to mix in rapidly, and I'd never claim it does not happen even then. It happens, and is no big deal. I said this decades ago. Abiotic precipitation happens all the time.

 

[Randy Holmes-Farley]

With bicarbonates, it's just that the bolus dosage briefly lowers the pH value, i.e. we produce a lot of CO2 and also carbonic acid. And this turns into a certain type of liquid called the dense liquid phase (you can google it).

Yes, bicarbonate dosing lowers pH when added. I'm glad FM finally agrees with me.

The dense liquid comment is trying to sound scientifically impressive. Not sure why it is brought up at all. It''s a highly detailed mechanistic idea on something we all agree on: calcium carbonate can precipitate.

When calcium carbonate is precipitating, scientists call the solution in the immediate vicinity of the surface a dense liquid phase. Giving the dimensions of the hydrated carbonate ions in angstroms would add just as much to the discussion.

Simulations Indicate Calcium Carbonate Has a Dense Liquid Phase

Computer simulations conducted at Berkeley Lab show show that calcium carbonate—the ubiquitous compound that is a major component of seashells, limestone, concrete, antacids and myriad other naturally and industrially produced substances—may momentarily exist in liquid form as it crystallizes...

cs.lbl.gov

"The simulations predict that in sufficiently supersaturated calcium carbonate solutions, nanoscale dense liquid droplets can spontaneously form. These droplets then coalesce to form an amorphous solid prior to crystallization."

 

[Randy Holmes-Farley]

And certain crystalline forms are formed that are stimulated by the particles in the tank and these in turn go back into solution bit by bit in order to reach this saturation point and that is this buffer battery.

A random hypothesis that lacks any supporting evidence, but if it were true, would seem likely for any alk additions of any type.

At high pH values ( i guess he means when we use hydroxide and carbonates supply systems) , we produce a lot of carbonates. The CO2 is bound there, sinks to the bottom and remains there. It does not dissolve because we maintain a high pH value.

Ah, so now higher tank pH is the enemy. I thought this was a benefit of bolus bicarbonate dosing: a significant pH boost.

What about all of those tanks that dose high pH additives and do not actually attain a high pH (due to high room CO2). They only attain a ph level similar to FM in the graph above. Or when the tank pH is even lower? They are fine? No broken buffer? No old tank symdrome? Apparently, they can all rest easy now.

Nevertheless, I do not doubt some added hydroxide in high pH tanks can end up as permanently deposited calcium carbonate in all sorts of places. Normal, expected (by me, having said so for years) and is not really a concern (to me). Does it waste some of the added calcium and alk? Likely yes in some scenarios. Is that a problem? I don't see why.

Carbonates no longer dissolve at pH 8.4-8.5. Although there is re-dissolution, this happens in the biofilms due to low pH values or the production of organic acids.
It is a misconception that the lime simply precipitates. It takes everything we have in the aquarium with it in terms of organic matter. Dyes, amino acids, food etc. and that's why all the dirt in the sand is black or brown."
.

Of course calcium carbonate at pH 8.4 in seawater doesn't dissolve, nor does it dissolve at pH 7.9. That's exactly what supersaturation means.

I don't appear to suffer from any misconception that FM claims about what may get into depositing calcium carbonate, although I think the term foods may be stretching things a bit. Little calcium carbonate pac men come to mind, gobbling up food particles. lol

 

[Randy Holmes-Farley]

Then he switches to the sand discussion.
If I have understood this correctly, it is not primarily about the precipitations when dosing carbonates and hydroxides, but generally about precipitations that no longer dissolve at high pH values (typical for lime water and carbonate dosing).
If, on the other hand, bicarbonate supplies are used, the precipitates are gradually dissolved due to the drop in pH value (i.e. healing of the broken buffer system).
I cannot understand this, perhaps others can.

I don't know what was claimed, but here are my thoughts...

Sand hardening is a classic problem in calcium carbonate precipitation, and it is by far most likely on new bare calcium carbonate sand. That is because all of the assorted things that bind to sand (organics, magnesium, phosphate, bacteria, etc.) are not yet fully in place to stop it from acting as seed crystals for more calcium carbonate precipitation.

Such precipitation is also far more likely at higher pH and higher alk due to the supersaturation factor going up rapidly as those rise. pH is a particular issue, with a 0.3 pH unit rise acting equivalently to a doubling of either calcium or alkalinity.

I don't think it is likely the effect has anything to do with redissolution not happening when the pH is high because I do not think that is why sand hardening is not apparent at lower pH, but in any case, sand hardening is a concern in new tanks (happened in mine) and folks experiencing it are encouraged to take action in the ways I post at least twice a week.

FWIW, sand does dissolve in reef tanks even those using only hydroxide. Folks who knew Larry Jackson from years ago frequently noted that he used kalkwaser as the sole source of calcium and alk, and over extended times had to periodically replace his sand because it slowly dissolved.

Overall, it sounds like the broken buffer system is now being blamed on calcium carbonate particles not redissolving, which seems odd. The oceans and reef tanks are filled with calcium carbonate (newly deposited as well as old materials) no matter what folks do and all seems well.

 

[GARRIGA]

Feel like at I'm an airport watching planes fly over my head clueless as to exactly how and why, however, seems one dose of formate lights out knowledge gained and might explain why others report slow readings on alkalinity. Give bacteria a chance to break the formate down ready for lights on although no affect on pH

 

[Randy Holmes-Farley]

In this new vid from Doug, he said he's adding 1.8 DKH but only getting a recorded 0.4DKH increase / consumption; I'll screenshot the chart;



Green is pH, grey is Alk;

Thanks, GARF.

As we've discussed throughout this thread, without a comparator that does not have the bolus dosing on the same system, and even assuming the KH director is accurate and they know correctly what alk they dosed (do they use the label claim?), I'm not sure how one can draw conclusions about the "alk plateau" coming from additions of alk (from, say, the hypothesized microcrystals settling on surfaces and later dissolving, offsetting demand) vs consumption of alk (say, by formation of such crystals, other abiotic precipitation, and biological consumption, not being particularly strong from 10:00-18:00).

 

[Pod_01]

In this new vid from Doug, he said he's adding 1.8 DKH

Just to add my observations on the Alk.

I been using FM Balling light and I was dosing about 70ml a day.
Going by this:

With my system having approximately 230L I estimate my consumption was 1.5 dKh a day. I newer did the calculation before, I dosed it as per FM recommendation, add if not enough add more etc… 1.5 dKh looks like a lot for what I have.

Anyways 4 weeks back I switched to TM Original Balling method (3 boxes of A, B and C). At this point I did the conversion based on the calcium consumption. I had enough of secret formula, disappearing Alk etc…
Anyways my calculations told me I need 70 ml of A and B and C.

So I been using 70ml of TM part B and my Alk is not dropping.

Based on my estimate 70ml of TM part B for 230L based on my estimate is 0.81 dKh.

I may be wrong, the math may be wrong. All I can say for me 1+1 doesn’t equal 2.
Maybe my system is still dissolving small particles of Alk LOL.

Just thinking out loud, but unbiased third party should be used to determine or validate the potency of the FM KH mix.

 

[Randy Holmes-Farley]

IMO, all theoretical arguments aside about what may or may not be happening after a bolus dose of bicarbonate or slow dosing of, say hydroxide or carbonate (no one using hydroxide does large single doses), what can we take away from their assertions?

Let's give FM the benefit of the doubt that the plateau in alk is from these hypothesized microcrystals redissolving. They would have then established that a once a day dosing could lead to more stable alk than was previously assumed.

How and why is that better than spread out dosing to attain stable alk at about the same pH?

 

[Randy Holmes-Farley]

Just to add my observations on the Alk.

I been using FM Balling light and I was dosing about 70ml a day.
Going by this:

With my system having approximately 230L I estimate my consumption was 1.5 dKh a day. I newer did the calculation before, I dosed it as per FM recommendation, add if not enough add more etc… 1.5 dKh looks like a lot for what I have.

Anyways 4 weeks back I switched to TM Original Balling method (3 boxes of A, B and C). At this point I did the conversion based on the calcium consumption. I had enough of secret formula, disappearing Alk etc…
Anyways my calculations told me I need 70 ml of A and B and C.

So I been using 70ml of TM part B and my Alk is not dropping.

Based on my estimate 70ml of TM part B for 230L based on my estimate is 0.81 dKh.

I may be wrong, the math may be wrong. All I can say for me 1+1 doesn’t equal 2.
Maybe my system is still dissolving small particles of Alk LOL.

Just thinking out loud, but unbiased third party should be used to determine or validate the potency of the FM KH mix.

Thanks, Garf. Very interesting comparison.

If I could summarize (check it please), and ask a question.

1. You dosed FM Balling then switched to TM Balling, and the calculated alk dose needed much less (bit over half as much) with the TM as with the FM product?

Was the alk maintained at the same level?

Seemingly that is consistent with a label claim issue on one or both products, and we have data suggesting a label claim issue with the FM product.

 

[carbl]

Ah, so now higher tank pH is the enemy. I thought this was a benefit of bolus bicarbonate dosing: a significant pH boost.

That was my first thought too.
But ultimately this train of thought makes his supply ideal.
Hydroxide/Carbonate dosing = higher pH BUT preciptitates that dont dissolve + broken buffer system, which leads in many cases to old tank syndrome.
Bolus with his bicarbonate = higher pH + dissolution of precipitates + repair of the buffer system.
Sounds great!

The crux of the matter is that something is being declared a problem, which in most cases it is not. Of course there are precipitations. Everyone can see that when you clean the pump, for example.
He also says that there are people who have great tanks with every system, even in the long term. They have the "blue thumb", but they are in the absolute minority.
There is always an answer that suits you.

At least I now understand how he derives his theses. You can believe it or not, but in any case the story about the missing bicarbonate is complete nonsense. It is simply not included in the stated quantity.
It is quite bizarre. In a youtube video, where 99% of the followers have no idea about chemistry, technical terms and explanations are thrown around. But in other social media, where there are people who have enough knowledge to understand the thoughts and theories, nobody from FM appears and discusses.

 

[Pod_01]

Thanks, Garf. Very interesting comparison.

If I could summarize (check it please), and ask a question.

1. You dosed FM Balling then switched to TM Balling, and the calculated alk dose needed much less (bit over half as much) with the TM as with the FM product?

Was the alk maintained at the same level?

Seemingly that is consistent with a label claim issue on one or both products, and we have data suggesting a label claim issue with the FM product.

Yup Alk is being maintained… I am using KH director and it was 8.5 with FM dosing 70 ml. It is 8.5 with TM Original Balling dosing 70 ml…

There are ups and downs as pH increases or drops. The swings are 8.5 dKh up to 9.2 dKh and back down. It may be related to KH director.

But general summary is I dosed 70ml KH with FM and I am dosing 70ml with TM part B.

I hope that helps.

 

[SDchris]

You add 2kh mathematically

Did they address the alkalinity mathematical dilemma on the label. Seems like everything is a mute point after that.

 

[Randy Holmes-Farley]

Yup Alk is being maintained… I am using KH director and it was 8.5 with FM dosing 70 ml. It is 8.5 with TM Original Balling dosing 70 ml…

There are ups and downs as pH increases or drops. The swings are 8.5 dKh up to 9.2 dKh and back down. It may be related to KH director.

But general summary is I dosed 70ml KH with FM and I am dosing 70ml with TM part B.

I hope that helps.

Ah, ok. So equal volumes dosed gives equal alk in the tank, but the label claims suggest that FM is dosing a lot more alk than the TM product at that matching volume.

Got it.