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Summary (the whole thing in one paragraph)
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). This can be verified with NH3 sensing films. ClorAm-X is an adduct of formaldehyde and sulfite, and partially dissociates into those two pieces in order to work, with the sulfite part responsible for dechlorination and both parts needed for the ammonia removal. Prime and other “ammonia neutralizer” products also contain the same chemical compound as ClorAm-X, or a similar compound - rongalite - an adduct of formaldehyde and sulfoxylate, or as in the case of Prime, are a mix of both compounds. These products can all be measured with titrations using bleach to quantify the sulfite/sulfoxylate dechlorinator and a subsequent titration for the formaldehyde after the dechlorinator is gone. The amounts of the active ingredients in recommended doses of these “ammonia neutralizer” products are small, safe doses that are far below the amounts actually needed to do anything measurable to remove ammonia.
Topic outline
Part 1: Ammonia neutralizer performance head to head
How much can these products actually reduce the amount of total ammonia in a sample of aquarium water? Do they all work similarly well at their recommended doses?
To evaluate this, 2ppm total ammonia in saltwater was treated with ClorAm-X, Prime, and Aqueon Ammonia Neutralizer. These three products represent two different but closely related chemicals: Hydroxymethanesulfonate (ClorAm-X), Rongalite (Aqueon), and a mix of the two (Prime). Each product was dosed at 1x and 10x of the standard dose - corresponding to the maximum allowed by the ClorAm-X label instructions. The maximum label-allowable doses of Prime and Aqueon products are not more than this. Measurements after 24 hours of reaction time were made via a Seneye NH3-sensing film that had been calibrated against known total ammonia and pH values. Measurements via NH3 sensor - film or ion selective electrode - is necessary to bypass the interference that these compounds and any other dechlorinator/reducer has on a chemical total ammonia test. Details on the seneye calibration and measurement work by @Dan_P can be found in this thread.
Figure 1 percent of 2ppm total ammonia remaining after 24 hours with 1x and 10x of three ammonia removal products. Red bar is the only data with statistically significant difference.
The amount (as a percent) of remaining total ammonia after 24 hours is plotted - with the control corrected to 100%. Given the measurements needed to generate these calculated values - free ammonia, pH, temperature - the uncertainty is larger than the differences between the control and any of the treatments, except for the 10x ClorAm-X.
This result seems to suggest that despite the similarity in active ingredients, only one of these products has detectable ammonia reduction under label usage conditions (if the detection attempts are very careful!). Let’s look closer at the performance details to determine under what circumstances actual ammonia reduction might be seen: when, at what dosages, and how much reduction?
Part 2: Details of ClorAm-X performance: dosage, amount reduction, time
For most of this section, we’ll focus on the most effective version of this product, ClorAm-X, which is chemically sodium hydroxymethanesulfonate (HMS for short) and later we’ll revisit what the other related chemicals do. We’ve done a number of tests previously, and failed to find detectable ammonia decrease - so this section is about demonstrating what conditions are actually needed for detectable ammonia removal to occur.
What does varying the dosage from low to well above the label amounts show for ammonia reduction?
In this test, the same setup as above was used, except that 10ppm total ammonia was present in the samples. Measurements via Seneye (calibrated against standards) were made at 24 hours.
Figure 2 Percent of 10ppm total ammonia remaining after 24 hours with 1x, 10x, 100x of ClorAm-X. Red bars for statistical significance.
As before the 1x dose of ClorAm-X does not remove ammonia enough to be detectable given the measurement uncertainties. A 10x and 100x dose both reduce ammonia by easily measurable amounts. But even these large doses (~320 and ~3200mg/L of HMS) do not remove substantially all of the ammonia. Regardless of the large amount of the product added - the ammonia removal is only partial.
Here’s the same trend illustrated by measurements done on many samples.
Figure 3 Total Ammonia remaining at 24 hrs plotted vs amount of HMS used. Blue data is 4:1 molar ratio of HMS:Ammonia, Green data is 85:1 molar ratio, and the Orange data is a fixed amount of HMS with varied levels of total ammonia. The x-axis is in mM of HMS with red numbers on the axis indicating how many multiples of the recommended label dosage are being used.
The trend here is clear, significant ammonia decrease is possible and certainly happens with this chemical - but only if guidelines about allowable maximum dosages are thoroughly exceeded. Red numbers on x-axis are multiples of recommended dose - 10x being the highest allowable by product instructions.
This can also be observed without a Seneye, using NH3 sensing films by seachem or others.
This is what 1ppm total ammonia looks like after ~2 days treated with a 30x dose of ClorAm-X. After 2 days, the pH was corrected to 7.6 in each 500mL sample for a couple of hours and then disks removed to the small plastic wells for the picture.
Figure 4 Total Ammonia removal detectable by seachem NH3-sensitive films. Left: just ammonia, center: no ammonia with ClorAm-X, right: ammonia+ClorAm-X.
While precisely quantifying the ammonia removal here based on these colors would be essentially impossible, it is roughly consistent with the measurements in Fig. 3 where 30x ClorAm-X might be expected to have somewhere around 50-70% of total ammonia remaining after 48 hours.
How does the ammonia removal progress with time?
Here’s what the ammonia removal rate looks like for total ammonia starting at ~8ppm when treated with ~50x dose of ClorAm-X and measured over 24 hours. For these measurements, pH was repeatedly corrected back to 8.0 so the measurements with the calibrated Seneye could be done in a consistent way.
Figure 5 Total Ammonia remaining (as a percent) vs time over 24 hours. About the same amount is removed in the first 3 hours as from 3 to 24 hours.
This amount of ClorAm-X is the same as the dosages that generated about 50% ammonia removal in Fig 3. It should be noted again that this dosage (50x) is far higher than the maximum allowable by label instructions (10x).
In the first hour, very little of the eventual effect has occurred. After 3 hours about half of the eventual 24 hour effect has taken place, meaning that a significant part of the desired reaction takes longer than 3 hours to occur.
(Part 3 & 4 tomorrow)
Parts 3 & 4 here
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). This can be verified with NH3 sensing films. ClorAm-X is an adduct of formaldehyde and sulfite, and partially dissociates into those two pieces in order to work, with the sulfite part responsible for dechlorination and both parts needed for the ammonia removal. Prime and other “ammonia neutralizer” products also contain the same chemical compound as ClorAm-X, or a similar compound - rongalite - an adduct of formaldehyde and sulfoxylate, or as in the case of Prime, are a mix of both compounds. These products can all be measured with titrations using bleach to quantify the sulfite/sulfoxylate dechlorinator and a subsequent titration for the formaldehyde after the dechlorinator is gone. The amounts of the active ingredients in recommended doses of these “ammonia neutralizer” products are small, safe doses that are far below the amounts actually needed to do anything measurable to remove ammonia.
Topic outline
- Part 1: Ammonia neutralizer performance head to head
- Part 2: Details of ClorAm-X performance: dosage, amount reduction, time
- Part 3: Why/How Does Cloram-X work? Chemistry of HMS
- Part 4: How are other products different? Chemistry of Rongalite compared to HMS
- Part 5: Why do other Products not work? Measurements of product ingredients.
- Part 6: Extras - Overdose toxicity concerns, nitrification effects. Test method interference.
Part 1: Ammonia neutralizer performance head to head
How much can these products actually reduce the amount of total ammonia in a sample of aquarium water? Do they all work similarly well at their recommended doses?
To evaluate this, 2ppm total ammonia in saltwater was treated with ClorAm-X, Prime, and Aqueon Ammonia Neutralizer. These three products represent two different but closely related chemicals: Hydroxymethanesulfonate (ClorAm-X), Rongalite (Aqueon), and a mix of the two (Prime). Each product was dosed at 1x and 10x of the standard dose - corresponding to the maximum allowed by the ClorAm-X label instructions. The maximum label-allowable doses of Prime and Aqueon products are not more than this. Measurements after 24 hours of reaction time were made via a Seneye NH3-sensing film that had been calibrated against known total ammonia and pH values. Measurements via NH3 sensor - film or ion selective electrode - is necessary to bypass the interference that these compounds and any other dechlorinator/reducer has on a chemical total ammonia test. Details on the seneye calibration and measurement work by @Dan_P can be found in this thread.
Figure 1 percent of 2ppm total ammonia remaining after 24 hours with 1x and 10x of three ammonia removal products. Red bar is the only data with statistically significant difference.
The amount (as a percent) of remaining total ammonia after 24 hours is plotted - with the control corrected to 100%. Given the measurements needed to generate these calculated values - free ammonia, pH, temperature - the uncertainty is larger than the differences between the control and any of the treatments, except for the 10x ClorAm-X.
This result seems to suggest that despite the similarity in active ingredients, only one of these products has detectable ammonia reduction under label usage conditions (if the detection attempts are very careful!). Let’s look closer at the performance details to determine under what circumstances actual ammonia reduction might be seen: when, at what dosages, and how much reduction?
Part 2: Details of ClorAm-X performance: dosage, amount reduction, time
For most of this section, we’ll focus on the most effective version of this product, ClorAm-X, which is chemically sodium hydroxymethanesulfonate (HMS for short) and later we’ll revisit what the other related chemicals do. We’ve done a number of tests previously, and failed to find detectable ammonia decrease - so this section is about demonstrating what conditions are actually needed for detectable ammonia removal to occur.
What does varying the dosage from low to well above the label amounts show for ammonia reduction?
In this test, the same setup as above was used, except that 10ppm total ammonia was present in the samples. Measurements via Seneye (calibrated against standards) were made at 24 hours.
Figure 2 Percent of 10ppm total ammonia remaining after 24 hours with 1x, 10x, 100x of ClorAm-X. Red bars for statistical significance.
As before the 1x dose of ClorAm-X does not remove ammonia enough to be detectable given the measurement uncertainties. A 10x and 100x dose both reduce ammonia by easily measurable amounts. But even these large doses (~320 and ~3200mg/L of HMS) do not remove substantially all of the ammonia. Regardless of the large amount of the product added - the ammonia removal is only partial.
Here’s the same trend illustrated by measurements done on many samples.
Figure 3 Total Ammonia remaining at 24 hrs plotted vs amount of HMS used. Blue data is 4:1 molar ratio of HMS:Ammonia, Green data is 85:1 molar ratio, and the Orange data is a fixed amount of HMS with varied levels of total ammonia. The x-axis is in mM of HMS with red numbers on the axis indicating how many multiples of the recommended label dosage are being used.
The trend here is clear, significant ammonia decrease is possible and certainly happens with this chemical - but only if guidelines about allowable maximum dosages are thoroughly exceeded. Red numbers on x-axis are multiples of recommended dose - 10x being the highest allowable by product instructions.
This can also be observed without a Seneye, using NH3 sensing films by seachem or others.
This is what 1ppm total ammonia looks like after ~2 days treated with a 30x dose of ClorAm-X. After 2 days, the pH was corrected to 7.6 in each 500mL sample for a couple of hours and then disks removed to the small plastic wells for the picture.
Figure 4 Total Ammonia removal detectable by seachem NH3-sensitive films. Left: just ammonia, center: no ammonia with ClorAm-X, right: ammonia+ClorAm-X.
While precisely quantifying the ammonia removal here based on these colors would be essentially impossible, it is roughly consistent with the measurements in Fig. 3 where 30x ClorAm-X might be expected to have somewhere around 50-70% of total ammonia remaining after 48 hours.
How does the ammonia removal progress with time?
Here’s what the ammonia removal rate looks like for total ammonia starting at ~8ppm when treated with ~50x dose of ClorAm-X and measured over 24 hours. For these measurements, pH was repeatedly corrected back to 8.0 so the measurements with the calibrated Seneye could be done in a consistent way.
Figure 5 Total Ammonia remaining (as a percent) vs time over 24 hours. About the same amount is removed in the first 3 hours as from 3 to 24 hours.
This amount of ClorAm-X is the same as the dosages that generated about 50% ammonia removal in Fig 3. It should be noted again that this dosage (50x) is far higher than the maximum allowable by label instructions (10x).
In the first hour, very little of the eventual effect has occurred. After 3 hours about half of the eventual 24 hour effect has taken place, meaning that a significant part of the desired reaction takes longer than 3 hours to occur.
(Part 3 & 4 tomorrow)
Parts 3 & 4 here
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