Does Prime actually "Detoxify" free ammonia, NH3?

[brandon429]

I found this prior video posted of the tank from December

Jawfish full recovery?

youtube.com

Prime didn’t have anything to resolve if that’s the system the non digital reading came from

 

[merkmerk73]

I found this prior video posted of the tank from December

Jawfish full recovery?

youtube.com

Prime didn’t have anything to resolve if that’s the system the non digital reading came from

That video was pretty old and was my system with 0 ammonia after the cycle - the fish recovered but then died in the overflow by getting mulched up somehow - I have since learned how to prevent this in future Pearly Jawfish acclimations (fish jail with a net)

Anwyay I hadn’t been testing for ammonia in weeks because I considered it solved

I had a suspicious fish death - expensive blue flasher wrasse - and decided to test a couple days after my weekly water change - I change out 20% minimum.

I was shocked to find ammonia in the third green reading from my Red Sea kit, tested two more times to confirm with API and Red Sea that it was .8

While I wasn’t sure what could have caused such an ammonia spike because my nitrates and phosphates have been low (see post about dinos) , this thread is what I found when I googled it prime works because I had immediately dosed it

All fish, coral, and inverts are fine and I have another 25% WC coming up today - just thought I’d report that after dosing prime last Saturday night that the ammonia test went way back down to .2

I didn’t dose prime yesterday so I’ll test again today

 

[taricha]

Short version: Does Prime have formaldehyde in it? Interesting Q, but pointless regardless because formaldehyde doesn't protect from ammonia even if it does react - the hypothetical product is toxic in aquaria conditions, and it looks likely it doesn't react with ammonia in aquaria anyway.

This is a rebuttal of sorts that I found on another forum. It will probably kill a few brain cells.

A Brief History of Prime

A BIG THANK YOU to @Guppysnail and @Odd Duck for this concept, for the editing of this article and for reviewing it for accuracy and errors! A Brief History of Prime® An abbreviated history of dechlorinators and detoxifiers and their evolution Discussions on whether dechlorination and detoxificat...

forum.aquariumcoop.com

As @Dan_P said, much of the underlying references are irrelevant (papers about what H2S, UV-A, Ozone, etc do to ammonia, reactions that happen with ammonia inside living organisms etc. )

But I'm apparently a glutton for punishment, so I thought this was interesting. And it is the chem forum so sifting through confusing and messy data is some people's idea of a good time.



That test from the above article seems to be an airborne Formaldehyde test like this one.
If the author simply held Prime nearby and detected formaldehyde, this might be a proper detection. If they did something less rigorous like adding a drop of Prime directly into the reaction liquid, then they might have just decomposed something else into formaldehyde. (It's not said which was done.)

Seachem contemplates formaldehyde in other people's products, but doesn't confirm or deny formaldehyde in it anywhere I could find.
@Randy Holmes-Farley has explained the role that formaldehyde would play in the proposed reaction of ClorAm-X that is expected to bind Ammonia.

(None of what follows is relevant to Prime if it doesn't actually have formaldehyde in it. I expect it is still relevant to ClorAm-X etc.)

This paper from 1978 analyzed the actual products in the reaction between formaldehyde and ammonia at 25C using NMR, so it would seem fairly ironclad that such a reaction actually occurs at room temp.
Structure and chemistry of the aldehyde ammonias. 3. Formaldehyde-ammonia reaction. 1,3,5-Hexahydrotriazine (abstract only)

@Malcontent had shared this paper about using formalin to detoxify ammonia for catfish and shrimp (fresh and saltwater) earlier in the thread.
They found the ratio of formalin to ammonia that's needed to react all the ammonia, then they used that ratio of formaldehyde to treat ammonia running up to 2ppm total ammonia.



What they concluded was that even though the ammonia was gone, fish and shrimp still died - thus the ammonia-formaldehyde product is still toxic (their conclusion.)
But they never compared ammonia+formalin to just ammonia without formalin. And their test for if the ammonia was in fact reacted away by the formaldehyde was ..."Ammonia concentration was determined by method recommended by Grassholf (1976)" - which if you look up that text, is in fact the salicylate total ammonia test.
So an alternative interpretation consistent with their data is that maybe the formaldehyde didn't actually react away the ammonia in the first place.

After reading that paper, I checked what 2ppm ammonia did with Formalin in their recommended dosage.
It kills off the total ammonia test to zero, but shows no reduction on the NH3 films.

Looks like one of two things could be going on that would be consistent with all the data I'm aware of:
One: Is it plausible that formaldehyde does react with ammonia, produces a compound that can still pass through the gas-permeable NH3 sensing films, fooling the films into thinking NH3 is unreacted, and the compound also is still toxic to aquatic life so the whole stupid thing is moot whether it binds it or not?

Or two: Is it more likely that the reaction between formaldehyde and ammonia is not actually a slam dunk in aquaculture settings, and the paper measuring the products with NMR was reacting ammonium hydroxide with formaldehyde in conditions (pH, concentration) that is different enough from aquaria, that perhaps those reactions in fact don't really occur for us to any great extent.

There is a 1995 paper that I think addressed the question really well.
"Tolerance to Formalin by a Fluidized-Bed Biofilter and Rainbow Trout Oncorhynchus mykiss in a Recirculating Culture System" see attached pdf.
They actually looked at the question of whether formaldehyde interferes with the test methods.

"Effects of formaldehyde on TAN (Total Ammonia Nitrogen) measurement by the Nessler method, the
salicylate method (using the Hach spectrophotometer), and an ammonia probe (Orion model 95-12) were also tested, by addition of 100 ppm formalin to one of a pair of samples of fish tank water before analysis."...
"The Nessler method was found to give an intense yellow color and erroneously high ammonia values in the presence of formaldehyde. Measurement of paired water samples with and without addition of 100
ppm formalin yielded 1 7.6 and 1.14 mg/L TAN (total ammonia nitrogen), respectively. The salicylate method failed to detect TAN in the presence of formaldehyde, giving readings of 0.0 and 1.0 mg/L TAN for paired samples with and without addition of 100 ppm formalin, respectively. However, ammonia probe measurements were not affected by 100 ppm formalin, indicating that ammonia and formaldehyde did not react under the conditions in the system."

 

[MnFish1]

One: Is it plausible that formaldehyde does react with ammonia, produces a compound that can still pass through the gas-permeable NH3 sensing films, fooling the films into thinking NH3 is unreacted, and the compound also is still toxic to aquatic life so the whole stupid thing is moot whether it binds it or not?

I don't care about formaldehyde per se - BUT - every test has a sensitivity and specificity etc etc - and Just because the Seachem tests are not sensitive enough (In my or your hands) - does not mean that in vivo enough ammonia (NH3) is being decreased to 'detoxify it'. As many people (including you - I think have said) - My guess is that MOST tanks - will detoxify ammonia anyway within x hours with no intervention. The only way I could hypothesize that Prime etc etc (the other products) can detoxify ammonia - is if they were able to bind it long enough for the tank itself to take over. I have had multiple discussion (and debates) - with Seachem - who continue to insist. - that Prime detoxifies ammonia and buys time.

I was tempted (key word) - having 2 tanks set up - in identical conditions - with saltwater acclimated FEEDER guppies. Then adding small amounts of ammonia - with measurements - until symptoms occurred. When/if they did - the control group would be left, and the experimental group would be treated with Prime - However - due to an outcry - I decided not to do this. But it's a pretty easy experiment to do. If the survival rate in the control tank vs the prime treated tank is significantly diferent and replicated - it would show Prime, etc - does detoxify ammonia - but not the mechanism.

 

[Randy Holmes-Farley]

I don't care about formaldehyde per se - BUT - every test has a sensitivity and specificity etc etc - and Just because the Seachem tests are not sensitive enough (In my or your hands) - does not mean that in vivo enough ammonia (NH3) is being decreased to 'detoxify it'. As many people (including you - I think have said) - My guess is that MOST tanks - will detoxify ammonia anyway within x hours with no intervention. The only way I could hypothesize that Prime etc etc (the other products) can detoxify ammonia - is if they were able to bind it long enough for the tank itself to take over. I have had multiple discussion (and debates) - with Seachem - who continue to insist. - that Prime detoxifies ammonia and buys time.

I was tempted (key word) - having 2 tanks set up - in identical conditions - with saltwater acclimated FEEDER guppies. Then adding small amounts of ammonia - with measurements - until symptoms occurred. When/if they did - the control group would be left, and the experimental group would be treated with Prime - However - due to an outcry - I decided not to do this. But it's a pretty easy experiment to do. If the survival rate in the control tank vs the prime treated tank is significantly diferent and replicated - it would show Prime, etc - does detoxify ammonia - but not the mechanism.

An in vivo head to head comparison would certainly be useful.

People have been challenging Seachem on this for years, and I recall one of them claiming Seachem threatened action against them, though i cannot find it now. Despite this public challenge, yet not once have they ever trotted out the evidence that you say they claimed to have.

One wonders why not.

 

[Dan_P]

The only way I could hypothesize that Prime etc etc (the other products) can detoxify ammonia - is if they were able to bind it long enough for the tank itself to take over.

This hypothesis does not explain how ”binding ammonia” does not actually reduce free ammonia in solution for any length of time. If the amount is below the detection limits we are working with then the bound amount of ammonia is also not enough to reduce toxicity.

I do agree that the aquarium’s ability to respond to ammonia is likely the reason ammonia spikes go away, and Prime plays absolutely no role whatsoever. Moreover, the aquarium has a massive defense system against ammonia toxicity: pH.

Ammonia spikes are actually total ammonia spikes with an unknown level of free ammonia. Because of the strong influence pH has on the amount of free ammonia for a given amount of total ammonia, most ammonia spikes could actually be harmless or at most a gill irritanting events, not life threatening events. Confusing total ammonia test results with the amount of free ammonia in solution has likely created an industry to sell a placebo to cure a non-event.

 

[Randy Holmes-Farley]

Confusing total ammonia test results with the amount of free ammonia in solution has likely created an industry to sell a placebo to cure a non-event.

That is my expectation.. Very few hobbyists know if their fish could or would actually die, and when it doesn’t, they credit the treatment. If it does die, they just assume ammonia was too high or the treatment was too late to help.

 

[merkmerk73]

This hypothesis does not explain how ”binding ammonia” does not actually reduce free ammonia in solution for any length of time. If the amount is below the detection limits we are working with then the bound amount of ammonia is also not enough to reduce toxicity.

I do agree that the aquarium’s ability to respond to ammonia is likely the reason ammonia spikes go away, and Prime plays absolutely no role whatsoever. Moreover, the aquarium has a massive defense system against ammonia toxicity: pH.

Ammonia spikes are actually total ammonia spikes with an unknown level of free ammonia. Because of the strong influence pH has on the amount of free ammonia for a given amount of total ammonia, most ammonia spikes could actually be harmless or at most a gill irritanting events, not life threatening events. Confusing total ammonia test results with the amount of free ammonia in solution has likely created an industry to sell a placebo to cure a non-event.

Yeah, maybe.

But anecdotally, I just took another ammonia reading and it was between 0 and 0.2

Nitrites were 0 and Nitrates were less than 10.

So I don't buy the "beneficial bacteria took care of your .8 ammonia spike"

There may just be more than we understand at play.

 

[Randy Holmes-Farley]

Yeah, maybe.

But anecdotally, I just took another ammonia reading and it was between 0 and 0.2

Nitrites were 0 and Nitrates were less than 10.

So I don't buy the "beneficial bacteria took care of your .8 ammonia spike"

There may just be more than we understand at play.

0.8 ppm ammonia that was fully converted to nitrate would give 3 ppm nitrate, so there's no apparent oddity to explain, even if every test measurement was perfectly accurate.

 

[merkmerk73]

0.8 ppm ammonia that was fully converted to nitrate would give 3 ppm nitrate, so there's no apparent oddity to explain, even if every test measurement was perfectly accurate.

Nah, the nitrate and nitrite readings were the same as before when my ammonia spiked.

I'm not saying that Prime did this, but the data from my test kits doesn't reflect that the tank just processed everything on its own - an ammonia spike like that without an obvious source (lots of dead stuff) should correspond to a nitrite spike too before converting to nitrates.

 

[MnFish1]

An in vivo head to head comparison would certainly be useful.

People have been challenging Seachem on this for years, and I recall one of them claiming Seachem threatened action against them, though i cannot find it now. Despite this public challenge, yet not once have they ever trotted out the evidence that you say they claimed to have.

One wonders why not.

Agree

 

[MnFish1]

This hypothesis does not explain how ”binding ammonia” does not actually reduce free ammonia in solution for any length of time. If the amount is below the detection limits we are working with then the bound amount of ammonia is also not enough to reduce toxicity.

I do agree that the aquarium’s ability to respond to ammonia is likely the reason ammonia spikes go away, and Prime plays absolutely no role whatsoever. Moreover, the aquarium has a massive defense system against ammonia toxicity: pH.

Ammonia spikes are actually total ammonia spikes with an unknown level of free ammonia. Because of the strong influence pH has on the amount of free ammonia for a given amount of total ammonia, most ammonia spikes could actually be harmless or at most a gill irritanting events, not life threatening events. Confusing total ammonia test results with the amount of free ammonia in solution has likely created an industry to sell a placebo to cure a non-event.

You miss the point entirely - sensitivity is the key..... IMHO

 

[MnFish1]

This hypothesis does not explain how ”binding ammonia” does not actually reduce free ammonia in solution for any length of time. If the amount is below the detection limits we are working with then the bound amount of ammonia is also not enough to reduce toxicity.

I do agree that the aquarium’s ability to respond to ammonia is likely the reason ammonia spikes go away, and Prime plays absolutely no role whatsoever. Moreover, the aquarium has a massive defense system against ammonia toxicity: pH.

Ammonia spikes are actually total ammonia spikes with an unknown level of free ammonia. Because of the strong influence pH has on the amount of free ammonia for a given amount of total ammonia, most ammonia spikes could actually be harmless or at most a gill irritanting events, not life threatening events. Confusing total ammonia test results with the amount of free ammonia in solution has likely created an industry to sell a placebo to cure a non-event.

agree - to most - except the pH in a given tank is usually stable. Thus - ph - comparing Hour 0 to Hour 12 is likely not to play a role (as an example)

 

[Randy Holmes-Farley]

Nah, the nitrate and nitrite readings were the same as before when my ammonia spiked.

I'm not saying that Prime did this, but the data from my test kits doesn't reflect that the tank just processed everything on its own - an ammonia spike like that without an obvious source (lots of dead stuff) should correspond to a nitrite spike too before converting to nitrates.

I don’t understand what you are saying, and I don’t really see an anomaly..

One would not necessarily see the nitrite before it became nitrate, you could have had 3 ppm nitrate and detected “less than 10 ppm”, and not all of the ammonia taken up needs to end up as nitrate. It may all have been taken up and used to make organics.

 

[MnFish1]

I don’t understand what you are saying, and I don’t really see an anomaly..

One would not necessarily see the nitrite before it became nitrate, you could have had 3 ppm nitrate and detected “less than 10 ppm”, and not all of the ammonia taken up needs to end up as nitrate. It may all have been taken up and used to make organics.

Which throws a wrench into what everyone says about ammonia - nitrite and nitrate - 'if'. BTW I don't disagree with you - just amplifying what you're saying

 

[merkmerk73]

I don’t understand what you are saying, and I don’t really see an anomaly..

One would not necessarily see the nitrite before it became nitrate, you could have had 3 ppm nitrate and detected “less than 10 ppm”, and not all of the ammonia taken up needs to end up as nitrate. It may all have been taken up and used to make organics.

I’m just reporting what happened over the past few days

Nitrate was the same color as it has been - barely above zero - and I’ve been tracking this for weeks because I’m having a low nutrient issue

My ammonia had a sudden spike which was confirmed over 3 test kits, I dosed prime aggressively, now it’s near 0 with no other change in other params

Maybe the tank handled it in one day with no detectable change in nitrate or nitrite, or maybe Prime had some beneficial effect

You seem to be aggressively dismissing this because it goes against the running hypothesis - I personally don’t have a dog in the fight and I’m just reporting what I’m seeing first hand

(This ammonia spike is what drove me to find this thread in the first place)

 

[Dan_P]

You miss the point entirely - sensitivity is the key..... IMHO

The analytical sensitivity of our experiments was greater than the minimum amount of free ammonia that the hobby assumes begins to be a problem for fish. And since the need to bind a high level of ammonia is important not a small amount, the use of the term sensitivity is unclear.

 

[Dan_P]

agree - to most - except the pH in a given tank is usually stable. Thus - ph - comparing Hour 0 to Hour 12 is likely not to play a role (as an example)

Not true. Many aquaria exhibit day/night pH swings and there is no 12 period during this swing when the pH is the same.

 

[Randy Holmes-Farley]

Which throws a wrench into what everyone says about ammonia - nitrite and nitrate - 'if'. BTW I don't disagree with you - just amplifying what you're saying

FWIW, I’m not sure the traditional nitrogen cycle has all that much to do with ammonia uptake and consumption in an operating reef tank.

 

[taricha]

Nah, the nitrate and nitrite readings were the same as before when my ammonia spiked.

I'm not saying that Prime did this, but the data from my test kits doesn't reflect that the tank just processed everything on its own - an ammonia spike like that without an obvious source (lots of dead stuff) should correspond to a nitrite spike too before converting to nitrates.

In a mature system, classic nitrification Ammonia->NO2->NO3 may be 3rd in importance behind 1) photosynthetic uptake, and 2) heterotrophic uptake (since algae release carbon that feed bacteria living on & around the algae, those two can't even be well separated).

I did some measurements I thought were interesting about this.
my 10+year old sandbed processed ammonia at 0.1-0.2 ppm ammonia/day into NO2->NO3. But my system overall could consume ammonia at anorder of magnitude faster rate ~anywhere from 2+ppm to 4ppm ammonia per day (with no NO2/NO3 release).
https://www.reef2reef.com/threads/d...nitrify-who-eats-ammonia-in-our-tanks.815803/