Bolus dosing

[Randy Holmes-Farley]

from the video, it claimed:
That's why we have nearly 3,000 people enjoying good pH in the tanks that they've never had before. Okay, so there's no way you can say it doesn't work uh because we've got the proof in the users.

Where did that number come from?

Surely they do not have data from 3,000 users that compared bolus to nonbolus dosing of the same materials, independent of lighting and other changes, and tracked pH effects over time.

We can hardly get a couple of folks to do this comparison, and it means those 3,000 are ignoring the other parts of the bolus method and deviating from FM directions relating to lighting.

Most likely, if the number reflects anything at all, it is the number of users who use this FM product at all.

 

[IntrinsicReef]

Not loving "IntrinsicReef said" above Doug's quotes (lol) but I am very glad you are refuting his claims in detail. I know you get this a lot, but thank you for using your knowledge to go up against the charlatans. I smelled bs, but don't have the knowledge to argue chemistry.

 

[Randy Holmes-Farley]

from the video, it claimed:
Okay, and there's a very special piece of chemistry which is um it was known as a kinetic constraint of um of carbon dioxide.

I do not doubt that there are lots of discussions of kinetic constraints related to CO2 and organism growth. CO2 does not instantly equilibrate with water (hence the daily swing in pH in reef tanks) and the whole idea of CO2 in planted freshwater tanks is that the CO2 is in short supply. Raising pH without raising alkalinity (as the bolus dose theory claims is happening) is inherently reducing the amount of CO2/carbonic acid present. If an organism needs to get CO2 from free CO2 (rather than bicarbonate, as many marine organisms do), then raising the pH makes it harder to do so.

Beyond that, I'm not seeing how the statement about kinetic constraints relates to the proposed mechanisms.

That said, the idea of kinetic constraint of carbon dioxide is SO SPECIAL that this thread (page 67 specifically) is the first or second hit on googling

"kinetic constraint" of carbon dioxide

Try it for yourself. That itself says something important.

Other hits are really off target, at least for the first two pages.

 

[Randy Holmes-Farley]

Not loving "IntrinsicReef said" above Doug's quotes (lol) but I am very glad you are refuting his claims in detail. I know you get this a lot, but thank you for using your knowledge to go up against the charlatans. I smelled bs, but don't have the knowledge to argue chemistry.

Sorry, I understand the concern. I'll try to address it by editing.

 

[Randy Holmes-Farley]

If we take the whole cobbled together mess as factual, doesn't that then mean that the effectiveness of "Bolus Dosing" in context to pH and this "timed release" stability has everything to do with exposed calcified surface area AND flow in any given system? What about algae covered... coralline covered, biofilm covered, etc? Those surfaces would appear to not fall into the magic zone.

I am sorry, but the crap just gets deeper and deeper and you would think at some point too deep... but alas they just invent more science and publish another video the next week. Layers and layers of crap.

The other seemingly obvious flaw is that if some of the dosed material is sequestered for several hours somehow and slowly released through some unclear mechanism, how is that different than spreading out the dosing of that same alk over the light cycle?

If what they propose is a cheap mans way of spreading out dosing without a dosing pump, that's one thing, but to claim other benefits that do not apply to spread out dosing (such as the purported pH boost effect) seem to fall into the category of having your cake and eating it too.

 

[BeanAnimal]

The other seemingly obvious flaw is that if some of the dosed material is sequestered for several hours somehow and slowly released through some unclear mechanism, how is that different than spreading out the dosing of that same alk over the light cycle?

If what they propose is a cheap mans way of spreading out dosing without a dosing pump, that's one thing, but to claim other benefits that do not apply to spread out dosing (such as the purported pH boost effect) seem to fall into the category of having your cake and eating it too.

Excellent and very intuitive observation and something that did not occur to me. The list of scientific and logical flaws in this entire method continues to grow.

 

[IntrinsicReef]

Thank you for the layman's explanation. One other question that might have been covered. Doug warns (I have also heard fears circulating in the community) about precipitates redissolving into the aquarium during power outages or equipment failures. Let's say a pH drop during a less than 24 hours event. Is there any truth in this? It seems like precipitates would have a hard time redissolving in a solution that is 7.9 instead of 8.3 for instance, especially in a short term scenario.

Randy, sorry if you addressed this, but do you have input on whether calcium carbonate or other precipitates will dissolve back into saltwater with a drop in pH typical of a day long power outage or equipment failure? I think the fear proposed is that bound elements ( copper etc) will be released into the water column at toxic levels. Thank you

 

[Randy Holmes-Farley]

Randy, sorry if you addressed this, but do you have input on whether calcium carbonate or other precipitates will dissolve back into saltwater with a drop in pH typical of a day long power outage or equipment failure? I think the fear proposed is that bound elements ( copper etc) will be released into the water column at toxic levels. Thank you

Aragonite is about 3x supersaturated in seawater at pH 8.1-8.2 and 6.5 dKH. Calcite is about 5x supersaturated.

If the pH drops by about 0.5 pH units, aragonite can just begin to slowly dissolve, but it will be very slow at that pH. Calcite would need a drop of 0.7 pH units.

Amorphous forms of calcium carbonate may form and then transform into one or the other of these, and it can dissolve at somewhat higher pH.

These are essentially the reasons I suggest that folks keep the pH at 7.8 or higher, and may also be why 7.7-7.8 is a common bottom end, because any further drop dissolves a bit of calcium carbonate, raising the pH back up.

 

[BeanAnimal]

I can attest to the self buffering not allowing things to get too far out of whack. I didn’t dose a single thing for over 5 years or do a water change and corals were still able to calcify.

 

[IntrinsicReef]

Aragonite is about 3x supersaturated in seawater at pH 8.1-8.2 and 6.5 dKH. Calcite is about 5x supersaturated.

If the pH drops by about 0.5 pH units, aragonite can just begin to slowly dissolve, but it will be very slow at that pH. Calcite would need a drop of 0.7 pH units.

Amorphous forms of calcium carbonate may form and then transform into one or the other of these, and it can dissolve at somewhat higher pH.

These are essentially the reasons I suggest that folks keep the pH at 7.8 or higher, and may also be why 7.7-7.8 is a common bottom end, because any further drop dissolves a bit of calcium carbonate, raising the pH back up.

That is very helpful. So, is it safe to assume that when the pH drops below 7.7 the calcium carbonate will dissolve equally from all sources exposed to water ( rock, sand, precipitate?)
There is a concern expressed in this interview and elsewhere that with more recent elevated trace dosing, that the calcium carbonate precipitate will bind elements that are toxic in relatively low amounts ( copper, flouride) and release with a low pH event.

 

[IntrinsicReef]

I can attest to the self buffering not allowing things to get too far out of whack. I didn’t dose a single thing for over 5 years or do a water change and corals were still able to calcify.

Absolutely. I use self buffering in freshwater tanks with limestone holey rock. The pH can dip pretty low in a month between cleanings without intervention.

 

[Randy Holmes-Farley]

That is very helpful. So, is it safe to assume that when the pH drops below 7.7 the calcium carbonate will dissolve equally from all sources exposed to water ( rock, sand, precipitate?)
There is a concern expressed in this interview and elsewhere that with more recent elevated trace dosing, that the calcium carbonate precipitate will bind elements that are toxic in relatively low amounts ( copper, flouride) and release with a low pH event.

I cannot answer that question as it relates to the precipitate proposed by FM because I do not know what chemical structure they are proposing (and I’m not sure they don't either since they use words like “little bicarbonate crystals”). I seriously doubt one can ever precipitate any bicarbonate crystals from seawater.

 

[trevorhiller]

Doug does go off in part of the interview about how Kalkwasser and Sodium carbonate sequester all of the the CO2 and there is not enough for coral photosynthesis. I have heard Craig Bingman mention this effect of Kalk in his talks on Kalkwasser chemistry, but it seems to be very extreme examples, and not likely to happen in an aerated box of water with animals living in it.

A little anecdote to backup your thinking...

I dose both the maximum possible saturated Kalkwasser (ie. full daily evaporation) plus sodium hydroxide to my tank. Several times I've had a snail get stuck on the intake of the skimmer and shut it down--greatly decreasing the aeration and thus the CO2 levels. This always causes the pH to go through the roof with the Kalk & the NaOH. Last time I hit high 8.6x.

In this example, I could see CO2 being limited in the tank. But otherwise it seems there is plenty of CO2 dissolving into the water keeping the pH in the low 8 range.

I also have a pretty large ERV in my house (~110 CFM on a 2,800 sqft house) and my CO2 level runs in the low 500 range (currently 520 at this moment according to my AirThings monitor). So even in spite of all these measures, it seems there is still ample CO2 getting into the system--even with the low ambient CO2. I imagine on the average tank without all these measures that would never happen.

 

[6272862829]

So is it known? If FM is using straight bicarbonate or a mixture? @Randy Holmes-Farley from my understanding bicarbonate cant raise up ph like they are describing. So how can they see ph gains with it or advertise ph gains ? Could they be using a mixture of bicarbonate and carbonate ?

 

[Randy Holmes-Farley]

So is it known? If FM is using straight bicarbonate or a mixture? @Randy Holmes-Farley from my understanding bicarbonate cant raise up ph like they are describing. So how can they see ph gains with it or advertise ph gains ? Could they be using a mixture of bicarbonate and carbonate ?

It is straight bicarbonate, as determined by IR spectroscopy and by alkalinity titration of a solution of the material (303.9 mg of the mix in 1 L ultrapure water) shows an alk of 10.02 dKH (done in duplicate).

Both tests match sodium bicarbonate.

For example, 303.9 mg of pure sodium bicarbonate is 3.618 millimoles of bicarbonate. Put that in 1 L, and the alk is 3.618 meq/l, which is exactly 10.13 dKH.

If there were any sodium carbonate present, the alk value would be higher than the measurement.

The pH effect (if any) likely comes from two things: the increased lighting early in the light cycle (which is a part of the method), and the simple boost of alk to a higher level at that time of day than may exist with 24/7 dosing.

On the last point, seawater equilibrated fully with air (any air) will have higher pH at higher alk. A boost of 20% in alk will result in a pH that is higher by about 0.08 pH units higher (after full equilibration with air).

The implication of that last effect is that if one uses bicarbonate to boost alk, there is a small pH drop on first adding it, then a small pH gain to higher than the start on aeration.

If one does the same thing with carbonate, there is a pH boost initially, then it drops back to the same point as the bicarbonate after aeration.

Finally, if ones uses hydroxide, there is an even bigger pH boost, then a bigger drop back to the same raised pH as the other two after full equilibration.

I have personally tested this expectation and published the data years ago at Advanced Aquarist magazine:

Chemistry And The Aquarium: The Relationship Between Alkalinity And pH

Randy answers many questions in this complex relationship.

reefs.com

Supplement	Initial pH	24 hour pH	120 hour pH
none	8.10	8.11	8.21
0.5 meq/L HCO3-	8.06	8.15	8.33
0.5 meq/L CO3–	8.44	8.28	8.34
0.5 meq/L OH-	8.76	8.47	8.33
0.5 meq/L H+	6.91	7.91	8.15

 

[6272862829]

It is straight bicarbonate, as determined by IR spectroscopy and by alkalinity titration of a solution of the material (303.9 mg of the mix in 1 L ultrapure water) shows an alk of 10.02 dKH (done in duplicate).

Both tests match sodium bicarbonate.

For example, 303.9 mg of pure sodium bicarbonate is 3.618 millimoles of bicarbonate. Put that in 1 L, and the alk is 3.618 meq/l, which is exactly 10.13 dKH.

If there were any sodium carbonate present, the alk value would be higher than the measurement.

The pH effect (if any) likely comes from two things: the increased lighting early in the light cycle (which is a part of the method), and the simple boost of alk to a higher level at that time of day than may exist with 24/7 dosing.

On the last point, seawater equilibrated fully with air (any air) will have higher pH at higher alk. A boost of 20% in alk will result in a pH that is higher by about 0.08 pH units higher (after full equilibration with air).

The implication of that last effect is that if one uses bicarbonate to boost alk, there is a small pH drop on first adding it, then a small pH gain to higher than the start on aeration.

If one does the same thing with carbonate, there is a pH boost initially, then it drops back to the same point as the bicarbonate after aeration.

Finally, if ones uses hydroxide, there is an even bigger pH boost, then a bigger drop back to the same raised pH as the other two after full equilibration.

I have personally tested this expectation and published the data years ago at Advanced Aquarist magazine:

Chemistry And The Aquarium: The Relationship Between Alkalinity And pH

Randy answers many questions in this complex relationship.

reefs.com

Supplement	Initial pH	24 hour pH	120 hour pH
none	8.10	8.11	8.21
0.5 meq/L HCO3-	8.06	8.15	8.33
0.5 meq/L CO3–	8.44	8.28	8.34
0.5 meq/L OH-	8.76	8.47	8.33
0.5 meq/L H+	6.91	7.91	8.15

So what is your overall thought of bolus ? Any benefit to it or sticking to the traditional way of dosing 2 part better in your opinion ?

 

[Randy Holmes-Farley]

So what is your overall thought of bolus ? Any benefit to it or sticking to the traditional way of dosing 2 part better in your opinion ?

I've not seen any reason to think a bolus dose is better in some readily quantifiable way than spread out dosing of the same additives, keeping similar alkalinity.

Beware of any vague claims and ask what it is being compared to.

If one bolus doses 2 dKH, from say, 6.5 to 8.5 dKH, what is the appropriate spread out dosing alkalinity to compare to?

Steady 6.5 dKH?
Steady 8.5 dKH?

Something in between? If so, what?

That also then leaves the question as to what effect is the lighting change having relative to the alk dosing change. None of it? Some of it? All of it?

While I think it somewhat unlikely that corals like a sudden burst in alk at the start of the day, I certainly cannot prove they do not prefer it without folks testing that hypothesis, and such tests seem very hard to find.

 

[6272862829]

I've not seen any reason to think a bolus dose is better in some readily quantifiable way than spread out dosing of the same additives, keeping similar alkalinity.

Beware of any vague claims and ask what it is being compared to.

If one bolus doses 2 dKH, from say, 6.5 to 8.5 dKH, what is the appropriate spread out dosing alkalinity to compare to?

Steady 6.5 dKH?
Steady 8.5 dKH?

Something in between? If so, what?

That also then leaves the question as to what effect is the lighting change having relative to the alk dosing change. None of it? Some of it? All of it?

While I think it somewhat unlikely that corals like a sudden burst in alk at the start of the day, I certainly cannot prove they do not prefer it without folks testing that hypothesis, and such tests seem very hard to find.

Thanks Randy.

 

[BeanAnimal]

Gasp - you mean using actual known and relatively simple science can explain what is being seen and it is not a complex system of magic invisible crystals, broken buffer systems, special magic bacteria stabilizing pH or any other of the fantastical claims that Claude Schumacher has imagined?

 

[6272862829]

Gasp - you mean using actual known and relatively simple science can explain what is being seen and it is not a complex system of magic invisible crystals, broken buffer systems, special magic bacteria stabilizing pH or any other of the fantastical claims that Claude Schumacher has imagined?

Lol