tropic marin np bacto balance

Hans-Werner

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Both polyphosphate and orthophosphate are known to bind well to calcium carbonate surfaces, and are both used in scale control for that reason

I found the article quite hard to read and understand. Finally for me the only possible contribution to our question of phosphate adsorption to calcium carbonate was:

"While mM concentrations are often too low to trigger significant
phosphate mineral formation in the presence of CaCO3 [27,28], higher (mM) phosphate
concentrations have been shown to cause phosphate mineralization [29]. In acidic and
neutral environments, the strong dissolution of calcium carbonate contributes to the interaction
between calcium and phosphate ions, resulting in calcium phosphate precipitates [30].
However, as pH increases, phosphate uptake gradually decreases due to inhibition of
calcium carbonate dissolution; this is consistent with the excess mass trend we see from
TGA data (Table 1), where the excess mass (due in part to phosphate uptake) is largest for
the most acidic orthophosphate treatment (pH 7).
...
Comparing the phase complexity of the orthophosphate-treated powders to the almost unchanged
SHMP-treated powders, it is apparent why polyphosphate is widely used as a
dispersant and anti-flocculant. It is worth noting that our 10 mM treatments are equivalent
to 6 g/L, which is a concentration orders of magnitude higher compared to other recent
studies [32]. Even with the high concentrations, we find that any secondary phosphate
phases are barely detectable with ATR-FTIR spectra, even after annealing. However, its
surface-specific interactions with calcium carbonate are poorly studied.

5. Conclusions
Our work compares aqueous polyphosphate and orthophosphate treatments on aragonite,
using similar phosphate concentrations throughout. Polyphosphate treatments not
only help to prevent against aragonite dissolution during exposure to water, but also
provide a slight increase in the thermal stability of aragonite concerning the conversion
to calcite. In contrast, orthophosphate triggers secondary phases to form during the treatments,
which leads to more complex thermal annealing behaviours."

Doesn't this suggest that uptake of orthophosphate is higher than of polyphosphate and more polyphosphate remains in solution? I have to say I am not sure whether it says that and whether it helps us.
 

Randy Holmes-Farley

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More phosphate may bind, but that does not mean it binds more strongly. I believe it does not for the reasons I gave above. I expect that strongly bound polyphosphate messes up the surface for further precipitation of either calcium polyphosphate or calcium carbonate. Exactly akin to what polyacrylate is known to do: bind strongly by coating the surface, not by forming a calcium polyacrylate crystal.
 

Randy Holmes-Farley

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In any case, I cannot really debate this topic further than this without knowing exactly what materials you use or especially, seeing actual data on them. The term polyphosphates can include all sorts of different things (including organics such as ATP), some of which may bind strongly and some of which may bind poorly.

I accept that you think that are less bound, they may be, and regardless, the degree of binding doesn't make them lack utility in dosing P.
 

Hans-Werner

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Is there a chance that hydrogen phosphate (HPO4)2- is removed in tanks by binding with Ca2+ ions?

If it is by binding to calcium carbonate surfaces we also would have to know how many charges remain at ph 8.0 to 8.3. In orthophosphate we mainly have (HPO4)2- as the species binding to calcium carbonate, right?
 

Randy Holmes-Farley

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Is there a chance that hydrogen phosphate (HPO4)2- is removed in tanks by binding with Ca2+ ions?

If it is by binding to calcium carbonate surfaces we also would have to know how many charges remain at ph 8.0 to 8.3. In orthophosphate we mainly have (HPO4)2- as the species binding to calcium carbonate, right?

I don't think that HPO4-- is the main binding form despite being the predominant form present.

1704896465382.png
In seawater

At any pH there is always an equilibrium mix of H3PO4, H2PO4-, HPO4-- and PO4---, no matter what binds, the ratio only depends on pH. So if PO4--- binds, all of them decline.

I expect that PO4--- binds much more strongly than these others based on known pH effects of total P binding to aragonite (graph below). If it was HPO4--, the binding would not decline from 8.2 to 7.3 since that form is increasing in that range and PO4--- is decreasing ( I believe the decline at higher pH is due to loss of exposed Ca++ by CO3-- binding to it, as has been shown for calcite in model fluids (Table 4 in second link below, solution #5).



FWIW, there are many other scenarios where it is believed that the nonpredominant form of P is what actually binds. Lanthanum precipitation of phosphate as LaPO4 in a reef aquarium, for example. The Ksp for precipitation of LaPO4 is so much lower than for other possible combinations that even though PO4--- is not the main form, it is the one that precipitates. I have shown this myself in a publication on phosphate binding to a polymer phosphate binder, where binding of HPO4-- best explains the data, despite H2PO4- being the predominant form in that lower pH setting
 

Hans-Werner

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I expect that PO4--- binds much more strongly than these others based on known pH effects of total P binding to aragonite (graph below). If it was HPO4--, the binding would not decline from 8.2 to 7.3 since that form is increasing in that range and PO4--- is decreasing ( I believe the decline at higher pH is due to loss of exposed Ca++ by CO3-- binding to it, as has been shown for calcite in model fluids (Table 4 in second link below, solution #5).
Thanks for this explanation.

I thought that PO4--- would be too low at pH 8.3 according to the graph here:

Distribution-of-phosphate-species-as-a-function-of-pH_W640.jpg
 

Randy Holmes-Farley

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Thanks for this explanation.

I thought that PO4--- would be too low at pH 8.3 according to the graph here:

Distribution-of-phosphate-species-as-a-function-of-pH_W640.jpg

That's a freshwater graph.

In seawater, there is far more PO4---:

The “simplest” form of phosphorus in seawater is inorganic orthophosphate (sometimes called Pi by biologists). It consists of a central phosphorus atom surrounded by four oxygen atoms in a tetrahedron (Figures 1 and 2). Three of these oxygen atoms can either have an attached hydrogen atom or carry a negative charge (Figure 2). The ratio of these different forms depends on the pH in seawater. At pH 8.1, seawater contains 0.5% H2PO4–, 79% HPO4— and 20% PO4—. At higher pH the equilibrium shifts toward more PO4— and less HPO4—. For a variety of reasons, especially including the ion pairing and consequent stabilization of PO4— by calcium and magnesium, there is far more PO4— in seawater than in freshwater at the same pH. This shift in phosphate species distribution with pH may seem esoteric, but it actually has important implications for such things as the binding of phosphate to calcium carbonate rock and sand, because the different forms bind to different extents.

 

Randy Holmes-Farley

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I don't want to derail this awesome discussion, but how many of these forms will show up on a typical acetic acid test kit? Is it the 20%?

All types of test kits should detect all of these forms. :)
 

Randy Holmes-Farley

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In the typical molybdate test, the sample is acidified and all of the forms become phosphoric acid:



What happens to this procedure: Ammonium molybdate and potassium antimonyl tartrate react in acidic solution with orthophosphate to form a heteropolyic acid (phosphomopydbic acid) which can be reduced by ascorbic acid to form an intense blue color, the absorbance of which is then measured at 885 nm spectrums.
 

jda

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Ok. Cool. It was going to be a nightmare if po4 tests could have different readings with different pH levels.
 

Waldek M.

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I have a different interpretation that I believe explains that observation, as opposed to stronger binding to calcium carbonate surfaces by orthophosphate.

The article you post is, I believe, talking about precipitation of calcium phosphate. It is true that calcium phosphate likely forms better crystals for ongoing precipitation of calcium and orthophosphate from calcium and orthophosphate or polyphosphate in the water.

Polyphosphate will chelate calcium and keep it dissolved, while orthophosphate will not. It is also harder to orient every polyphosphate exactly into the right position to form the most highly stable crystals for ongoing precipitation. It's a basic idea that it is hard to form crystals of larger, more floppy molecules, especially if the molecules precipitating potentially come in a variety of actual chain lengths, preventing good crystal formation.

But that is not the scenario that I am concerned about, which is the binding of phosphate or polyphosphate to calcium carbonate surfaces. The potential for crystal formation says nothing about how well these molecules absorb onto existing calcium carbonate surfaces, and, IMO, polyphosphate is likely to bind more strongly, not less so, due to a known effect called polyvalency where the polyphosphate has multiple points of contact with the mineral surface, while orthophosphate does not, enhancing the binding of the polyphosphate.


"Moreover, polymers exhibit a phenomenon called “polyvalency” when multiple repeating units of the polymer can bind to multiple complementary cell receptors or viral proteins simultaneously. As multiple individual ligand–receptor interactions act synergistically, polyvalent interactions are typically much stronger than monovalent binding"
interesting discussion. I have a question: is it possible to have a large export of phosphates after an overdose of calcium carbonate? I'm asking because I gave too much and before the administration my phosphates had been stable for a month at the level of 0.2ppm, and after the administration they dropped to 0.03? I will add that the water cloudiness lasted for 2-3 days
 

Randy Holmes-Farley

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interesting discussion. I have a question: is it possible to have a large export of phosphates after an overdose of calcium carbonate? I'm asking because I gave too much and before the administration my phosphates had been stable for a month at the level of 0.2ppm, and after the administration they dropped to 0.03? I will add that the water cloudiness lasted for 2-3 days

Over dose of what exactly?
 

Naturalreef

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I used Bacto balance for over a year and my take----

A bottle lasts a long time as you have to dose very little. So it's economical.

At the 6 month mark I experienced a rise of P04 that kept rising while N03 stayed stable. When I got above .30 I used GFO to knock it back down. I was always chasing down the P04.

My goal when I started was to find a replacement product that I didn't have to use GFO. It didn't keep a balance as they claim.

I never used the Elimi-NP and had no intention to alternate and chase P04 all the time.

I didn't dose any bacteria as TM claims you don't need to.
---------------------------------

On Sunny he's doing a Zeo/ bacto balance combo.........mostly Zeo products so I really don't consider the Bacto balance integral. You could use vinegar in it's place and probably accomplish the same thing with his combo.
Did you try raising your dose of Bactobalance when your PO4 kept rising? Curious if increasing BB= more carbon= more PO4 reducing bacteria? I’m new to these products and so far am really liking Plus-Np and Bactobalance on a Sps dominant tank.
 

Waldek M.

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Over dose of what exactly?
I added too much calcium carbonate in the coral snow diy recipe and the white water stayed there for two days. I also added coral food from KZ. All the corals were rather happy and I didn't notice any stress in the fish, but only a large drop in phosphates, so I started to wonder what was causing it. Maybe a coincidence? I feed the corals quite heavily, but during the overdose period I stopped and maybe that's why the decline?
 

Hans-Werner

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I added too much calcium carbonate in the coral snow diy recipe and the white water stayed there for two days. I also added coral food from KZ. All the corals were rather happy and I didn't notice any stress in the fish, but only a large drop in phosphates, so I started to wonder what was causing it. Maybe a coincidence? I feed the corals quite heavily, but during the overdose period I stopped and maybe that's why the decline?
It is quite an old method of precipitating phosphate out of the water column to oversaturate the water with calcium carbonate until it precipitates and binds and coprecipitates phosphate.

So yes, it was most likely the formation of calcium carbonate precipitates that removed the phosphate.
 

Big E

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Did you try raising your dose of Bactobalance when your PO4 kept rising? Curious if increasing BB= more carbon= more PO4 reducing bacteria? I’m new to these products and so far am really liking Plus-Np and Bactobalance on a Sps dominant tank.

No, I followed the directions that were given by Tropic Marin. Not sure that makes sense what your saying as it's adding PO4 to the system. Maybe if the N03 had bottomed out to zero that might be a different case.
 

Naturalreef

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No, I followed the directions that were given by Tropic Marin. Not sure that makes sense what you’re saying as it's adding PO4 to the system. Maybe if the N03 had bottomed out to zero that might be a different case.
Some people were dosing more to find a balance is the reason I asked.
 

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