A Deep Dive on Ammonia Neutralizer Chemistry - Prime, ClorAm-X, Rongalite and friends.

[laughing tang]

@Dan_P I think your message got lost...

 

[Dan_P]

@Dan_P I think your message got lost...

Nah, just fat fingers on the iPad

See below for reprint. By the way, at a pH around 7.8 it is possible for a total ammonia of 0.3 ppm to have a free ammonia concentration near 0.005 ppm.

The Seneye unit calculates the total ammonia to be 20 ppb which is 0.02 ppm. If the Seneye temperature and pH are not accurate, or the free ammonia reading is off, this calculation will be off as well.

If Erase CL is a dechlorinator, this could cause the Hanna Checker to read low. I would trust the Checker for measuring total ammonia if a declorinator is not used.

And yes, if Erase CL lowers the pH, free ammonia will decline.

 

[laughing tang]

Nah, just fat fingers on the iPad

See below for reprint. By the way, at a pH around 7.8 it is possible for a total ammonia of 0.3 ppm to have a free ammonia concentration near 0.005 ppm.

The Seneye unit calculates the total ammonia to be 20 ppb which is 0.02 ppm. If the Seneye temperature and pH are not accurate, or the free ammonia reading is off, this calculation will be off as well.

If Erase CL is a dechlorinator, this could cause the Hanna Checker to read low. I would trust the Checker for measuring total ammonia if a declorinator is not used.

And yes, if Erase CL lowers the pH, free ammonia will decline.

Ha. I was going to say that but did not want to be rude . The temp is slightly off as is PH but not substantially. I think my confusion is (pardon me, I totally failed chemistry and math in school, making this a tricky hobby):

NH3 0.005 ppm
NH4 0.0203 ppm
for a total ammonia nitrogen of 0.0253.

This does not make any sense to me. If NH3 is 0.005, given my PH and temp, TAN should be 0.16 ppm when I use the Hamza total ammonia calculator. It seems to be a whole digit off, which seems more than say PH is 7.83 instead of 7.75. Temp is also usually only off by less than 0.5. Could that really cause the TAN to be one digit off?

I use hydros probes for PH and temp and I have found no way to get the seneye to match those, so would that not make the ammonia readings on the Seneye useless?

 

[Dan_P]

Ha. I was going to say that but did not want to be rude . The temp is slightly off as is PH but not substantially. I think my confusion is (pardon me, I totally failed chemistry and math in school, making this a tricky hobby):

NH3 0.005 ppm
NH4 0.0203 ppm
for a total ammonia nitrogen of 0.0253.

This does not make any sense to me. If NH3 is 0.005, given my PH and temp, TAN should be 0.16 ppm when I use the Hamza total ammonia calculator. It seems to be a whole digit off, which seems more than say PH is 7.83 instead of 7.75. Temp is also usually only off by less than 0.5. Could that really cause the TAN to be one digit off?

I use hydros probes for PH and temp and I have found no way to get the seneye to match those, so would that not make the ammonia readings on the Seneye useless?

The amount of free ammonia is profoundly affected by pH, and to a lesser but still important degree, temperature.

Play with this calculator to see how free (NH3) and total ammonia are affected by pH and temperature.

Free Ammonia Calculator

Aquarium calculator; Estimate the free (un-ionized) ammonia (NH3) concentration, given the total ammonia concentration.

www.hamzasreef.com

 

[laughing tang]

Thanks Dan. Yeah I did and plugged in the numbers from the screenshot (and SG 1.0026) and it came up to 0.17 ppm TAN. I do not understand how seneye shows 0 02. It is a mystery to me.

 

[Dan_P]

Thanks Dan. Yeah I did and plugged in the numbers from the screenshot (and SG 1.0026) and it came up to 0.17 ppm TAN. I do not understand how seneye shows 0 02. It is a mystery to me.

When I use the Seneye to measure free ammonia, I calibrate it against a standard.

 

[taricha]

Detail is Seneye NH3 lowers from 0.005 to 0.002 when I dose Erase CL. I suspect it's because of the pH decrease it causes. Thanks Dan.

Yeah I did and plugged in the numbers from the screenshot (and SG 1.0026) and it came up to 0.17 ppm TAN. I do not understand how seneye shows 0 02. It is a mystery to me.

I agree with you that the reported NH3 and NH4 values in that seneye screenshot don't make sense in relation to each other based on the other seneye measured parameters, and a calculator like hamza.
They probably only make sense in that they are very close to zero and are simply method noise around zero.

As he says, Dan found that the seneye he used did need calibration against known standards of total ammonia+pH to give accurate values.

When I use the Seneye to measure free ammonia, I calibrate it against a standard.

In your setup right now @laughing tang your total ammonia is dealing with an interfering compound, and your seneye might need some unknown correction/calibration curve. So we can't really say that either is accurate.

But the seneye trend is good information (even without a calibration curve), it's reading essentially "noise near zero" now and if it started to rise, that would indicate ammonia increasing.

 

[laughing tang]

Thank you both for that information. I would be very interested in details in how to calibrate the seneye, when hopefully I can finally get the clownfish juveniles into a cycled system and can dispense with Erase CL. As with the boxfish in the other post I am trying to get off the erase CL train.

For the clownfish tank, I have Hanna testing, erase CL dosing, water changes stats going back to February when we collected the larvae in my copious notes if it is of any interest. One can argue that if erase CL did nothing and the Hanna test is inaccurate, that data is useless; still the trends might be of value.

 

[Randy Holmes-Farley]

Thank you both for that information. I would be very interested in details in how to calibrate the seneye, when hopefully I can finally get the clownfish juveniles into a cycled system and can dispense with Erase CL. As with the boxfish in the other post I am trying to get off the erase CL train.

For the clownfish tank, I have Hanna testing, erase CL dosing, water changes stats going back to February when we collected the larvae in my copious notes if it is of any interest. One can argue that if erase CL did nothing and the Hanna test is inaccurate, that data is useless; still the trends might be of value.

What ammonia values are you concerned with that needs measurement? None of those you post seem a concern.

 

[laughing tang]

What ammonia values are you concerned with that needs measurement? None of those you post seem a concern.

Hi Randy, thank you. I don't want to detail the thread entirely beyond the seneye readings; this is a tank with clownfish juveniles where I have managed ammonia with Erase CL and Hanna testing, and I happen to also have a Seneye in this tank, which is why this tread peaked my interest. In an effort to get off the binder train I have added a 30 gallon sump and larger skimmer. With that TAN still rises so added turbostart last Saturday. Ammonia seems to be stabilizing at 0.40 the last 2 days.

Seneye typically shows Nh3 0.005-6 prior to twice daily dosing of Erased CL. Skimmer and filtration is off for 5 days due to Turbostart. After Erase CL NH3 is 0.002 after an hour or so, largely due to the PH decrease I presume. Nitrites are increasing now quite a bit (200 ppb this am) so I presume it's cycling. Seachem disk is yellow.

Basically I am just trying to get through the 5 day period without the skimmer and my readying the 75 gallon tank system in the next few days. They are overcrowded in this 20 gallon tank plus 30 gallon sump.

 

[Randy Holmes-Farley]

Hi Randy, thank you. I don't want to detail the thread entirely beyond the seneye readings; this is a tank with clownfish juveniles where I have managed ammonia with Erase CL and Hanna testing, and I happen to also have a Seneye in this tank, which is why this tread peaked my interest. In an effort to get off the binder train I have added a 30 gallon sump and larger skimmer. With that TAN still rises so added turbostart last Saturday. Ammonia seems to be stabilizing at 0.40 the last 2 days.

Seneye typically shows Nh3 0.005-6 prior to twice daily dosing of Erased CL. Skimmer and filtration is off for 5 days due to Turbostart. After Erase CL NH3 is 0.002 after an hour or so, largely due to the PH decrease I presume. Nitrites are increasing now quite a bit (200 ppb this am) so I presume it's cycling. Seachem disk is yellow.

Basically I am just trying to get through the 5 day period without the skimmer and my readying the 75 gallon tank system in the next few days. They are overcrowded in this 20 gallon tank plus 30 gallon sump

I would not be convinced that there is any concern:

How toxic is ammonia, really?

In the context of trying to understand why so many people believe Seachem Prime was useful for them in an elevated ammonia situation, against the data in the link below about Prime potentially doing nothing to free ammonia in seawater, the question arises, why...

www.reef2reef.com

 

[laughing tang]

I would not be convinced that there is any concern:

How toxic is ammonia, really?

In the context of trying to understand why so many people believe Seachem Prime was useful for them in an elevated ammonia situation, against the data in the link below about Prime potentially doing nothing to free ammonia in seawater, the question arises, why...

www.reef2reef.com

Thanks Randy, I did read that and was very surprised. Part of my confusion is due to an issue with our boxfish (disease forum) where the vet suspected ammonia and Erase CL for his symptoms and a person here said 0.12 TAN might have caused his symptoms. He did get up to 0.66 at the high point for a day. In any case, the comment about 0.12 TAN obviously set me on the wrong foot.

I would love though to be able to get my seneye properly calibrated. I've pretty much ignored it because I could not make sense of the readings.

 

[taricha]

Here's details on the amount of interference in a total ammonia test with the chemicals in question. Total ammonia of 2.0 ppm. Unmodified API total ammonia test, added 0.05, 0.10, and 0.30 mM concentrations of Formaldehyde, sulfite, HMS, Rongalite, and Prime (HMS+Rongalite mix).

For this API test, Formaldehyde and Sulfite interfere to essentially the same degree per mole. HMS interferes more, as it is formaldehyde+sulfite. Rongalite interferes the most, as it it formaldehyde + sulfoxylate, which the sulfoxylate can dechlorinate 2x as much as sulfite. and Prime being a mix of rongalite and HMS interferes to an extent somewhere between HMS and rongalite.
Formaldehyde of 0.3mM is the common recommendation (humblefish) for an in-tank 7-10 day treatment.
1x dose of ClorAm-X and of Fritz ACCR = 0.24 mM
1x dose of Prime is roughly 0.033 mM

The exact amount and manner of interference depends on the amount of reagents in the test, and how much excess. So a test from Red Sea, Hanna, or Hach could be interfered with more or less than API depending on how much excess reagents are provided in the test. Red Sea for instance has less chlorine than API, so the test interference would be larger than what's shown in the graph.

 

[Formulator]

Just saw this interesting observation from a member who I assume uses tap water for top off. What do you think is the explanation?

My worst crash came when I ran out of api water treatment and started using prime to treat my top off water, in less then 3 weeks every inch of my tank was GHA. I have since bought more api and the gha is receding

Post in thread 'Most tank crashes are caused by this….'
https://www.reef2reef.com/threads/most-tank-crashes-are-caused-by-this….1066793/post-12754955

 

[taricha]

Just saw this interesting observation from a member who I assume uses tap water for top off. What do you think is the explanation?



Post in thread 'Most tank crashes are caused by this….'
https://www.reef2reef.com/threads/most-tank-crashes-are-caused-by-this….1066793/post-12754955

my first, likeliest answer is that nothing in this report or anything else I'm aware of about Prime or API tap water conditioner makes that make sense.

but an unlikely answer is that 1x recommended dose of Prime would contain 0.032 mM of mixed HMS+rongalite, and rapidly dechlorinate 0.052 mM of Cl2.
The max value expected from tap water might be (EPA max) 4ppm Chlorine, or 0.056 mM of Cl2. which will be essentially = neutralized instantly based on my numbers above. But If someone had a badly degraded bottle of Prime, that has been opened, thus exposed to new O2, inverted over and over for a long time - this dechlorination ability would drop.
So it's possible that a very old often used bottle of Prime used according to standard minimum directions doesn't dechlorinate the full amount in tap water.
Addition of residual chlorine/chloramine through tap water to a reef tank might have unpredictable undesirable consequences.

 

[Flame2hawk]

Someone smarter then me reminded that…

Prime doesn't claim to remove ammonia.


"Prime® may be used during tank cycling to alleviate ammonia/nitrite toxicity. It contains a binder which renders ammonia, nitrite, and nitrate non-toxic, allowing the biofilter to more efficiently remove them."

It doesn't mention removal anywhere at all.

So are we saying withe this study that the binder which renders ammonia non toxic is not effective in Prime? Need some clarity as I’m a bit confused. Thx

 

[Randy Holmes-Farley]

Someone smarter then me reminded that…

Prime doesn't claim to remove ammonia.


"Prime® may be used during tank cycling to alleviate ammonia/nitrite toxicity. It contains a binder which renders ammonia, nitrite, and nitrate non-toxic, allowing the biofilter to more efficiently remove them."

It doesn't mention removal anywhere at all.

So are we saying withe this study that the binder which renders ammonia non toxic is not effective in Prime? Need some clarity as I’m a bit confused. Thx

Yes, it does not work as Seachem claims, and Seachem’s suggested way to test for it working shows it to not work.

 

[ISpeakForTheSeas]

So are we saying withe this study that the binder which renders ammonia non toxic is not effective in Prime? Need some clarity as I’m a bit confused. Thx

Yeah - to summarize it briefly:

-The binder theoretically works, but nowhere near effectively enough to be useful for ammonia removal in our tanks.

-The binder itself seems to be more toxic than the ammonia it's attempting to bind.

-Tests showing that the binder bound useful amounts of ammonia are explained by test kit interference caused by the chemicals involved in the binding process.

The longer description below (figure 11 is particularly helpful here):

in part 5 I can describe how to test for them, what was found, and why the products don't work even though the chemicals used actually do theoretically bind ammonia.

In part 5 we see that the amount of HMS / rongalite provided is far too small to achieve a significant ammonia removal effect (Fig 11), but if it were overdosed well beyond the recommended dosage (Fig 12) then it would remove measurable ammonia. So why not simply add more, and far exceed the allowed label maximum dosages - for instance using 30x ClorAm-X instead of the maximum recommended of 10x?

Apparently, toxicity concerns of such a high ammonia remover dose are not simply theoretical. A study that tested Prime in shipping bags [11] found that fish treated with approximately this level of Prime (0.5% by volume = 6.5 mM of combined HMS+rongalite) suffered toxicity “Although no ammonia accumulation was detected in the bag amended with the chemical ammonia remover, one fish was deceased, and another fish would have perished without intervention.” The fish - banggai cardinals - both suffered toxicity/mortality within 24 hours, even though O2 was kept over 70%, and pH stayed in the 7’s - while all fish in other treatments including untreated ammonia appeared normal for 3 days.

In Part 1 it was discussed briefly that HMS and rongalite create significant difficulty in correctly measuring ammonia due to interference with various chemical tests. There are a large number of sources of all kinds - from patents [6] to hobby product descriptions [12][13][14][15], aquaculture publications[16][17], and academic publications [18],[19],[20],[21],[11],[22] etc… that either explicitly or implicitly suggest that a salicylate total ammonia test is appropriate for measuring ammonia when treating with HMS or rongalite. Despite these sources, there is in fact significant interference with the salicylate total ammonia method that makes such measurements unreliable.

The formaldehyde itself interferes with the functioning of the salicylate ammonia test kit and shows erroneously low values for ammonia - small amounts can have considerable interference as shown below.

The lowering of the measured value of ammonia is significant, but formaldehyde does not actually remove ammonia or bind it in a meaningful way. This was previously demonstrated in fig. 8 where formaldehyde alone did not actually cause any lowering in the true ammonia level - unless it was accompanied by sulfite to complete the reaction scheme involving HMS from the thesis by Brown[4].

 

[Flame2hawk]

I suppose Clor AM X is good for saltwater aquariums as It’s sold as a freshwater pond product.?? Pls confirm.

All of this seems to suggest we’d be better off adding Fritz turbo900 at an aggressive rate to decrease ammonia?

 

[ISpeakForTheSeas]

I suppose Clor AM X is good for saltwater aquariums as It’s sold as a freshwater pond product.?? Pls confirm. Thx

It's not good enough to be useful, but chemically it's the same as/similar to saltwater products:

Thus far we have focused mostly on Hydroxymethanesulfonate (HMS), the ingredient in ClorAm-X as it is the most measurably effective ammonia remover of these types of compounds, but there is another commonly used aquarium chemical for these dechlorinator/ammonia remover applications - Hydroxymethanesulfinate also known as Rongalite. These are confusingly similar, differing by just one oxygen - at least one aquarium ammonia remover product MSDS lists the name of one compound, but the CAS number of the other. Despite many similarities there are a few important differences, a table below attempts to organize some relevant properties. (The sodium salts of each are the most common and are what is in aquarium usage)

Table 1. A list of relevant properties of the very similar compounds HMS and rongalite, used in aquarium ammonia remover products.

ClorAm-X is the best-performing of a barely effective product concept. Under the label usage ClorAm-X (but not Prime, or other common products) can be measured to lower the amount of total ammonia in a saltwater sample. This process is slow (24-48hr), requires high amounts of product (hundreds of mg/L of active ingredient), and incomplete (~50% ammonia removal is typical).

As mentioned, in high enough quantities to remove/bind useful amounts of ammonia, the binder becomes toxic.