Pressure on False Claim Products

[Js.Aqua.Project]

The issue with most of the recommendations and mentions so far on this thread would be not easily measuring alk in “meq” and not “dkh” / dose in the PH booster products

For the average reefer that’s the issue. And possibly companies can go further with offering this information on websites with dosing recommendations

In this case, why would it matter what unit we are testing in? Either the product does what it claims to or it doesn't.

Plus, most manufacturers provide references in both meq/l and dKH.

 

[taricha]

One technical way to accomplish #1 is to have a chemical that binds CO2 and for which the product is not titrated in an alkalinity test. I’m just not aware of any dissolved chemical that can do that.

Binding bicarbonate could have the desired effect of reducing alk and raising pH (exactly the opposite effect of dosing bicarbonate). But again, the product has to not be detected by an alk test.

Anyone have any wild ideas?

On wild ideas ..this doesn't sound plausible at all as a product, but I wonder if you had lanthanum hydroxide, would it dissolve in water, raising the pH, then precipitate as lanthanum carbonate taking the created alk down with it out of solution? That would seem to narrowly meet the technical claim, if it happened.

 

[Randy Holmes-Farley]

On wild ideas ..this doesn't sound plausible at all as a product, but I wonder if you had lanthanum hydroxide, would it dissolve in water, raising the pH, then precipitate as lanthanum carbonate taking the created alk down with it out of solution? That would seem to narrowly meet the technical claim, if it happened.

You are right, that would fit the technical claim. Whether it is lanthanum or some other material, going in as hydroxide and rapidly precipitating as a carbonate (and not an oxide) would meet the needs of something that raised pH and not alk.

It needs two things to happen;

1. Sufficient lanthanum hydroxide solubility to exist in the bottle

2. Sufficiently rapid precipitation of lanthanum carbonate to count as not adding alk.

I’ll have to work through the numbers later, but #1 is potentially a problem for lanthanum . This sort of paper can help supple values to consider:

Google Scholar

scholar.google.com

 

[Randy Holmes-Farley]

it should also be easy to see if there is any precipitate in testing .

Sodium and potassium hydroxide will transiently precipitate magnesium hydroxide, but at pH 8.5 or lower, it will not remain.

 

[Randy Holmes-Farley]

Lanthanum clearly fails the solubility requirement by many orders of magnitude.

This paper shows that the solubility of lanthanum hydroxide at any pH above 9.5 is less than 10-9 M (easiest to see in Figure 1 or 3) which is far, far too low to have any detectable effect on seawater alkalinity if the amount in the Brightwell directions is used. 10-9 molar, if all precipitated as lanthanum carbonate (La2(CO3)3) is effectively 3/2 x 10-9 M in its ability to remove carbonate, or 2 x 3/2 x 10-9 molar = 0.00000003 M or 0.000003 meq/L = 0.0000084 dKH in alkalinity removal.

Then dilute that at the max dose, 10 ml per 10 gallons (37,854 mL) and the alk reduction capability is reduced to 0.0000000022 dKH

"Do not add more than 10 ml per 10 gallons per day! "

https://www.sciencedirect.com/science/article/abs/pii/S0009254198000898

The solubility of lanthanum hydroxide will be further reduced in the presence of other hydroxides, the sodium and potassium hydroxides that Brightwell says are in it, but I think we need not worry about that.

I picked the pH of 9.5 and up from the graph in the paper (which is near the highest pH measured) because if the pH is not well above this value, the hydroxide is not going to be present in sufficient quantity to be able to significantly raise the pH of seawater. We know this from a variety of means, such as the pH raising effect of kalkwasser or simple hydroxide addition (my experiment). Kalkwasser (at about pH 12.5) has about 1000 times as much hydroxide in it as this solution would at pH 9.5. Would anyone think that 0.01 mL of kalkwasser (1/1,000th of the max dose of boost pH +) added to 10 gallons of seawater will have a significant pH raising effect? Certainly it does not.

The paper also suggests that the solubility of the lanthanum can be increased by having acetate present (0.026 M) but the solubility is still lower than the acetate concentration (less than 0.0001 M at pH 8.5; Figure 7 top , and so the added alk from the acetate metabolism would increase the alk more than the lanthanum would reduce it.

 

[taricha]

Just to clarify, I try to make "taricha brand pH++ that Totally Doesn't Raise Alkalinity for Real"....

If I take an NaOH solution to raise pH, and decide I can add a specific concentration of very soluble Lanthanum Chloride to the bottle to precipitate the right amount of Carbonate from saltwater to make it an alkalinity balance with the alk increase from NaOH - it would fail because La would not stay as LaCl and precipitate in my product bottle as hydroxides etc, and make the bottle a slurry that is extremely low in solubility. I think?

And setting Lanthanum aside - it's possible to imagine a product that could try to get around the physical laws requiring pH raising solutions to also raise alkalinity by using a loophole of precipitating the alkalinity added. But it would be super obvious that this loophole is what was being exploited because it'd have to create lots of insoluble precipitate. I think?

 

[jda]

Occams razor, right? I would not work too hard on this - you all are likely right.

As for LC, the effect on po4 dropping too fast would likely ruin your company. People can test for this an pay attention to po4.

Ran across a different product yesterday. TM claims that their Aluminum Oxide phosphate remover permanently binds po4. Is this possible with Al2O3? I have seen many, many places that it binds and unbinds to equilibrium with the outside environment like GFO, Aragonite, Calcite, Dolomite and other things. Glad to be wrong on this one...

 

[taricha]

As for LC, the effect on po4 dropping too fast would likely ruin your company. People can test for this an pay attention to po4.

Yeah, my product line would be called "Devil's Bargain" and all the products are designed to fix minor problems by creating much larger ones.

 

[rtparty]

Like a good murder mystery, the simplest explanation is often the correct one.

Misleading claims/outright lies while trying to exploit some marketing loophole is the simplest explanation here and not out of norm for the companies in question

 

[Randy Holmes-Farley]

Just to clarify, I try to make "taricha brand pH++ that Totally Doesn't Raise Alkalinity for Real"....

If I take an NaOH solution to raise pH, and decide I can add a specific concentration of very soluble Lanthanum Chloride to the bottle to precipitate the right amount of Carbonate from saltwater to make it an alkalinity balance with the alk increase from NaOH - it would fail because La would not stay as LaCl and precipitate in my product bottle as hydroxides etc, and make the bottle a slurry that is extremely low in solubility. I think?

And setting Lanthanum aside - it's possible to imagine a product that could try to get around the physical laws requiring pH raising solutions to also raise alkalinity by using a loophole of precipitating the alkalinity added. But it would be super obvious that this loophole is what was being exploited because it'd have to create lots of insoluble precipitate. I think?

Yes, adding lanthanum chloride to sodium hydroxide should result in white mud.

Yes, such a proposed mechanism must necessarily result in a precipitate that must settle out.

 

[Miami Reef]

Like a good murder mystery, the simplest explanation is often the correct one.

Misleading claims/outright lies while trying to exploit some marketing loophole is the simplest explanation here and not out of norm for the companies in question

Agreed. I don’t think it’s worth spinning our wheels to invent and create new laws in physics. Similarly to Vibrant’s “new” bacteria when it was just rebottled AlgaeFix. These companies aren’t that smart.

 

[Randy Holmes-Farley]

Occams razor, right? I would not work too hard on this - you all are likely right.

As for LC, the effect on po4 dropping too fast would likely ruin your company. People can test for this an pay attention to po4.

Ran across a different product yesterday. TM claims that their Aluminum Oxide phosphate remover permanently binds po4. Is this possible with Al2O3? I have seen many, many places that it binds and unbinds to equilibrium with the outside environment like GFO, Aragonite, Calcite, Dolomite and other things. Glad to be wrong on this one...

One might argue that the amount bound is always unchanged (even with individual ions frequently coming on and off) as long as the concentration of phosphate is unchanged.

Of course it can come off into lower phosphate water.

 

[jda]

One might argue that the amount bound is always unchanged (even with individual ions frequently coming on and off) as long as the concentration of phosphate is unchanged.

Of course it can come off into lower phosphate water.

That is a long way from "never will be released" in any case and even further away for a product that is supposed to be lowering phosphate.

 

[TokenReefer]

A good argument for taking the time to build foundational understanding of things. Even for laymen (non chemists) to know what is happening when it is happening. Not that I do all the time but I strive to...

 

[rtparty]

One might argue that the amount bound is always unchanged (even with individual ions frequently coming on and off) as long as the concentration of phosphate is unchanged.

Of course it can come off into lower phosphate water.

@Hans-Werner @Lou Ekus

Might as well bring this product into the discussion and get TM's response

 

[Randy Holmes-Farley]

Actually - this was going to be my question - could it be that though it chemically raises alkalinity 'some' - that that some is not large enough to be significant. I.e. using stoichiometry, it's easy to see that a certain chemical reaction will increase or decrease something. But - lets say the alkalinity goes up from 8.1 -->8.3 - thats not a significant rise, Right?

Now I’m even more concerned the issue is that they may not consider the effect of hydroxide on alk to be significant since they are using an alk test that cannot detect the expected rise from hydroxide alone.

Experimental testing of Brightwell Boost pH +

This is the proposed experiment: take some reef tank water, that is in the pH range that needs raising, say, pH 7.8 to 8.2, and has alkalinity in the range you suggest (7.7 to 10 dKH) some artificial seawater that is in the pH range that needs raising, say, 7.8 to 8.2, and has alkalinity in...

www.reef2reef.com

 

[Miami Reef]

Now I’m even more concerned the issue is that they may not consider the effect of hydroxide on alk to be significant since they are using an alk test that cannot detect the expected rise from hydroxide alone.

Experimental testing of Brightwell Boost pH +

This is the proposed experiment: take some reef tank water, that is in the pH range that needs raising, say, pH 7.8 to 8.2, and has alkalinity in the range you suggest (7.7 to 10 dKH) some artificial seawater that is in the pH range that needs raising, say, 7.8 to 8.2, and has alkalinity in...

www.reef2reef.com

How much is the alkainity expected to rise with a pH increase of 0.3? Using hydroxide, of course.

 

[Randy Holmes-Farley]

I will port any important results in testing Brightwell Boost pH plus to this thread, as needed, but for now I’ll keep most of the testing discussion and results in the testing thread.

Jack did some testing already and I posted it there. He also indicated he would be willing to reimburse folks buying the product just for this testing by giving them some other product they may want or provide it directly .

Normally, a company directly providing a product would be frowned upon for testing, but in this case I’m not concerned because the concern is not how potent a product is, but whether any product can accomplish what is claimed. But getting it from a third party is likely better anyway.

If you want help from Brightwell to do this testing, just post to the testing thread and I’ll figure out how to proceed based on numbers of folks, etc.

Experimental testing of Brightwell Boost pH +

This is the proposed experiment: take some reef tank water, that is in the pH range that needs raising, say, pH 7.8 to 8.2, and has alkalinity in the range you suggest (7.7 to 10 dKH) some artificial seawater that is in the pH range that needs raising, say, 7.8 to 8.2, and has alkalinity in...

www.reef2reef.com

 

[Devisissy]

While I do appreciate the effort on this battle (?) fight, whatever. I also find it equally hilarious. The entirety of half of these companies is junk science or good science applied wrong. Here is a junk stat, 93% of this hobby is based on false claims. With certain companies being a bigger offender. It's not just the products either, some people famous in this hobby are nothing more than con men. It's fascinating. You would have to make it a full time job to go after all these claims one by one. Then why stop there? Go after food, cosmetics, pharmaceutical. This is the equivalent of one mosquito on the back of a bull. It does nothing. There is no greater harm than time wasted.

 

[Randy Holmes-Farley]

How much is the alkainity expected to rise with a pH increase of 0.3? Using hydroxide, of course.

Thus is what I wrote to Jack:

When I have added 1.4 dKH worth of hydroxide to new IO, the pH boost was 0.67 pH units. While extrapolation is not perfect, it suggests that the alk rise for a 0.1 pH unit boost in that water should be roughly 0.2 dKH. I don’t think the API kit, when used as directed, can detect that.