How does Prime detoxify ammonia and nitrite?

[Tony Thompson]

Applicant Tiffani Furlough
Applicant Kevin A. Senkevech
Grantee Fritz Industries, Inc.
Primary examinerRobert A. Hopkins
Application number10854613KindB1Document number7097773

 

[Tony Thompson]

Hmmm...

What is even more interesting is the details of the methods used to determine the supposed reductions. This is given in much more detail in the Fritz patent and the paper submitted.

What also has to be considered in the document you attached, is that is a statement from ARG, the manufacturer of the original Amaquel. It could be noted that the new product Amaquel + which is not manufactured by ARG could be seen as a direct competitor to their product. A note should also be made of the fact that the documents I attached relate to Fritz Industries.

 

[Malcontent]

What is even more interesting is the details of the methods used to determine the supposed reductions. This is given in much more detail in the Fritz patent and the paper submitted.

What also has to be considered in the document you attached, is that is a statement from ARG, the manufacturer of the original Amaquel. It could be noted that the new product Amaquel + which is not manufactured by ARG could be seen as a direct competitor to their product. A note should also be made of the fact that the documents I attached relate to Fritz Industries.

It sounds like Fritz used Hach's colorimetric methods instead of ion chromatography. Same mistake Kordon made although Kordon used hobby grade kits. Kordon still persists in their claims that AmQuel Plus detoxifies nitrite/nitrate. Apparently, nobody in this industry is afraid of deceptive advertising class actions.

 

[Randy Holmes-Farley]

Although the more recent product by Kordon, Amaquel + (Amquel plus) also states to "detoxify" other Nitrogen Polyatomic Ions such as NO2- and NO3-.

Maybe all that means is that those are nontoxic already, so it accomplishes it automatically. lol

 

[Randy Holmes-Farley]

Finally found the Patent application, Gives a detailed description of the product I believe to be both in Seachem and Aquael Plus. Patent is applied for by Fritz Industries Inc.

The full document can be found here https://patents.justia.com/patent/7097773

Some extracts from the document below

"It has been discovered that a water soluble reducing agent comprised of a sulfur-containing, organic compound selected from alkali metal and alkaline earth metal formaldehydesulfoxylates can be used in a process to decrease the concentration of pollutants which are dissolved in saline and fresh water. The method of this invention, featuring the use of the mentioned compound, is particularly useful to reduce the concentration of pollutants dissolved in water used to contain and maintain live fish, such as aquariums. For purposes of the method of this invention, a pollutant is defined to specifically include ammonia, chlorine, chloramines, nitrite ions and nitrate ions. Furthermore, the mentioned compound, when employed in accordance with the method of this invention, can reduce the concentration of the pollutants to levels which are not believed to be toxic to fish."


"The compound useful herein reduces the concentration of chloramines, chlorine, ammonia, nitrites and nitrates in saline and fresh waters, and, when used in accordance with the method of this invention, reduces the concentration of these pollutants to levels which, it is believed, are not toxic to fish which are held in the treated water."

"The treating material is a sulfur-containing, reducing agent, and, more specifically, is a water soluble, sulfur-containing, organic compound selected from alkali metal and alkaline earth metal formaldehydesulfoxylates. The sulfur component of the sulfur-containing organic compound exhibits a valence of +4. The treating material is not known to be toxic to fish."

"It must be understood that the treating material does not remove the pollutants from water, the pollutants are, instead, converted to reaction products which are not known to be toxic to fish. The method of this invention is still further comprised of removing the reaction products from the water by appropriate means, such as by biological filtration."

"The reaction mechanisms between the treating material of this invention and nitrite and nitrate anions and the products of the reactions are also not known. However, treating water containing nitrites and nitrates in accordance with the method of this invention produces a decrease in the concentration of nitrites and nitrates dissolved in the water treated."

"A laboratory experiment was performed to determine the ability of sodium formaldehydesulfoxylate to reduce the concentration of chlorine, chloramines, ammonia, nitrites and nitrates dissolved in water."

"
The concentrations of free chlorine, chloramines, ammonia, nitrites and nitrates in the test sample were determined before addition of the treating material and 10 minutes after addition of all the treating material was completed. The results are set forth in Table 1.



TABLE 1 CONCENTRATION, ppm (See Footnote 1) POLLUTANT INITIAL FINAL REDUCTION Free chlorine 0.24 0.00 0.24 Chloramines 2.18 0.01 2.17 Ammonia 3.42 1.46 1.96 Nitrite 2.28 0.17 2.11 Nitrate 27.72 13.64 14.08 Footnote 1 The concentration of pollutants in the test sample was determined by methods described in Hach Water Analysis Handbook, 2nd Edition, 1992. Free and total chlorine, P. 761; Ammonia, Salicylate Method, P. 781; Nitrite, Diazotization Method, P. 784; Nitrate, Cadmium Reduction Method (High Range), P. 783.



Footnote 1

• • The concentration of pollutants in the test sample was determined by methods described in Hach Water Analysis Handbook, 2nd Edition, 1992. Free and total chlorine, P.761; Ammonia, Salicylate Method, P. 781; Nitrite, Diazotization Method, P.784; Nitrate, Cadmium Reduction Method (High Range), P. 783."

@Randy Holmes-Farley any comments would be greatly appreciated.

Tony Thompson, Sustainable Marine Aquatics

Formaldehyde sulfoxylate is the same material as hydroxmethanesulfonate that I showed above for Amquel (see discussion of this chemical in the link below). I don't have reason to think it is present in Prime since it is not consistent with what they say is in it.

Rongalite - Wikipedia

en.wikipedia.org

 

[Tony Thompson]

Maybe all that means is that those are nontoxic already, so it accomplishes it automatically. lol

I thoroughly I agree that the word used by the manufacturer "detoxify" is certainly one that requires relevance.

The statement in the patent abstract talks more about "reduction" of NO2 and NO3 and by significantly measurable percentage.

In the abstract, they give an explanation of the procedures of their test and boldly present their findings as showing data that they argue appears to show a conclusive reduction.

How accurate this data is and whether their is interference in the testing methods, is far above my knowledge of Chemistry.

Kordon make a point of explaining that there is a distinct difference between their original product, Amaquel and Amaquel +. The new product is also manufactured for them by an alternative company than the original.

It seems distinctly possible to me that their is some coloration between the claims of Seachem and Amaquel+ in the fact that both products claim a reduction in both NO2 and N03. Both parties also state that the reaction was not expected and has no current explanation.

I realise that without more detail from the parties concerned, that this discussion is rather impotent, therefore I thank you for your explanation and whish you good day. Best Wishes.

 

[Malcontent]

There's an ion chromatography lab near me if you really want to know...

But why stop there? Let's crowdfund sending Prime off to a deformulation lab.

 

[Jay Hemdal]

After a little more research I found this USA patent.

METHOD AND PRODUCT FOR REMOVAL OF CHLORAMINES, CHLORINE AND AMMONIA FROM AQUACULTURE WATER 75

Inventor: John F. Kuhns, Kansas City, Mo. 73)
Assignee: Aquascience Research Group, Inc., North Kansas City, Mo. (21)
Appl. No.: 738,481 22
Filed: May 28, 1985

OTHER PUBLICATIONS Blasiola, George C., "Chloramines', Pet Age, Jul., 1984, pp. 25-26. Herwig, Nelson, "Toxic Chloramine Induced Intravas 11 Patent Number: 45) Date of Patent: 4,666,610 May 19, 1987 cular Hemolytic Anemia in Fish', Freshwater and Ma rine Aquarium, 5(10), pp. 11-13, 91-92, 1982. Wheaton, Fredrick Warner, Aquacultural Engineering, pp. 608-612, 1977. Allied Chemical Corporation, "Dechlorination', 1977. Helz, George R. and Lynn Kosak-Channing, "Dechlo rination of Wastewater and Cooling Water', Environ. Sci & Tech., 18(2), pp. 48A-55A, 1984. Morrison, Robert T. and Robert N. Boyd, Organic Chemistry, 2nd edition, pp. 639-641, 1966. Walker, J. Frederic, Formaldehyde, 3rd edition, pp, 219, 251-253, 486-488, 621-623, 638, 1975. Primary Examiner-Peter Hruskoci Attorney, Agent, or Firm-Kokjer, Kircher, Bradley, Wharton, Bowman & Johnson 57

ABSTRACT A process for neutralizing chloramines, chlorine and ammonia in marine and fresh waters by adding an alkali metal formaldehydebisulfite in a dry or solution form in which the alkali metal formaldehydebisulfite is selected from the group consisting of sodium formaldehydebi sulfite and potassium formaldehydebisulfite. Preferably, the alkali metal formaldehydebisulfite is sodium formal dehydebisulfite added in the amount at least equal to the greater of the quantity required to react on a one to one molecular basis with 4 times the stoichiometric amount of ammonia, 12 times the stoichiometric amount of monochloramine, 10 times the stoichiometric amount of dichloramine or 12 times the stoichiometric amount of chlorine in the form of hypochlorites present in the water to be treated.

Full test here https://patentimages.storage.googleapis.com/9d/8d/7d/82bd73cbbe0819/US4666610.pdf

John is still around, I’m on Facebook with him, but last PM I sent him about Amquel went unanswered.
Jay

 

[Garf]

Don’t know why, but I thought it was this;
But with a big mark up.

 

[Tony Thompson]

John is still around, I’m on Facebook with him, but last PM I sent him about Amquel went unanswered.
Jay

Thanks Jay, unfortunately I was using the document authored by John Kuhns, with respect to the effects on NH3 by the standard product referred to as Amaquel.

The second abstract I linked, which suggested the reduction of NH3, NO2- and NO3-, was submitted by:
Tiffani Furlough (Balch Springs, TX), Kevin A. Senkevech (Terrell, TX) This makes the same claims as the product Amaquel Plus and Seachem Prime.

This document can also be found here https://www.mysciencework.com/patent/show/process-treating-water-US7097773B1

 

[Randy Holmes-Farley]

(PDF) Effect of Sodium Hydroxymethanesulfonate on Ammonia and Related Water Quality Parameters

PDF | A Sodium Hydroxymethanesulfonate product (ClorAm-X®, AquaScience Research Group Inc., USA) was used in water from a recirculating holding system... | Find, read and cite all the research you need on ResearchGate

www.researchgate.net

A Sodium Hydroxymethanesulfonate product (ClorAm-X®, AquaScience Research Group Inc., USA) was used in water from a recirculating holding system tank after 8 days Channel Catfish holding experiment with Total ammonia nitrogen (TAN) 15.8 mg/L. Three treatments; T1-50% the recommended dose (15.95 mg/L of ClorAm-X® for 1mg/L of total ammonia), T2-recommended dose (31.9 mg/L of ClorAm-X® for 1mg/L of total ammonia) and T3-150% of recommended dose (47.85 mg/L of ClorAm-X® for 1mg/L of total ammonia) were applied in 10 liters of water, each with three replications. Three replications of control without ClorAm-X® application were also used. 30 minutes post application, TAN, Nitrite, Nitrate, unionized ammonia and pH were measured using HACH® kits, spectrophotometer and pH meter. Results show that the product is effective in reducing TAN and unionized ammonia in concentration dependent manner. Nitrite and pH were not affected by treatments but nitrate increases slightly with increasing dose of ClorAm-X®. Increase of nitrate may be of concern only in seriously heavy doses of the product. Thus, Sodium Hydroxymethanesulfonate can be used in reducing ammonia content in recirculating holding systems where ammonia buildup is one of concern.

 

[Tony Thompson]

(PDF) Effect of Sodium Hydroxymethanesulfonate on Ammonia and Related Water Quality Parameters

PDF | A Sodium Hydroxymethanesulfonate product (ClorAm-X®, AquaScience Research Group Inc., USA) was used in water from a recirculating holding system... | Find, read and cite all the research you need on ResearchGate

www.researchgate.net

Just to clarify my personal comprehension. ClorAm X and Amquel (original) where both produced by ARG. or Aquascience Technologies, LLC.

I have not discovered any claims by ARG that either of these products reduce NO2 or NO3.

However , Kordons more recent product, Amquel+ (which was not manufactured by by ARG) is advertised as reducing both NO2 and NO3. Similar to the statement by Seachem with regards their product (Prime)

The only documentation I can find that gives any detail as to both the efficacy and testing procedures of a product, based on the same predominant active ingredient Formaldehyde sulfoxylate (or its synonyms). That also claim to reduce both NO2 and NO3, is the one covered by the patent of Fritz Ind. (I posted earlier). This is the patent I am most interested in.

Although at least one ingredient is mentioned in the patent abstract, Formaldehyde sulfoxylate, (or its synonyms), there may be further ingredients, or reactions that are not obviously apparent to myself or are beyond my extremely limited knowledge of Chemistry.

With regards my own personal conclusion on whether the product, (not a single ingredient within that product), in question is capable of such ambiguous statements, simply draws my suspicion that the same ingredients or processes may be related to the Seachem Product.

My question, is it feasible, likely or unlikely, that the Seachem product is based on the same patent as applied by Fritz Ind.

 

[Randy Holmes-Farley]

Just to clarify my personal comprehension. ClorAm X and Amquel (original) where both produced by ARG. or Aquascience Technologies, LLC.

I have not discovered any claims by ARG that either of these products reduce NO2 or NO3.

However , Kordons more recent product, Amquel+ (which was not manufactured by by ARG) is advertised as reducing both NO2 and NO3. Similar to the statement by Seachem with regards their product (Prime)

The only documentation I can find that gives any detail as to both the efficacy and testing procedures of a product, based on the same predominant active ingredient Formaldehyde sulfoxylate (or its synonyms). That also claim to reduce both NO2 and NO3, is the one covered by the patent of Fritz Ind. (I posted earlier). This is the patent I am most interested in.

Although at least one ingredient is mentioned in the patent abstract, Formaldehyde sulfoxylate, (or its synonyms), there may be further ingredients, or reactions that are not obviously apparent to myself or are beyond my extremely limited knowledge of Chemistry.

With regards my own personal conclusion on whether the product, (not a single ingredient within that product), in question is capable of such ambiguous statements, simply draws my suspicion that the same ingredients or processes may be related to the Seachem Product.

My question, is it feasible, likely or unlikely, that the Seachem product is based on the same patent as applied by Fritz Ind.

I was just reinforcing the idea that aminomethanesulfonate (aka formaldehyde sulfoxylate) doesn't detoxify nitrate with data from someone who actually measured it.

I have no idea what Seachem basis their Prime nitrate claim on, and I suspect it is inaccurate. Nitrate is pretty resistant to most types of chemistry, hence the reason a nitrate kit needs a special reducing agent to reduce it to nitrite before detecting it.

 

[Tony Thompson]

I was just reinforcing the idea that aminomethanesulfonate (aka formaldehyde sulfoxylate) doesn't detoxify nitrate with data from someone who actually measured it.

I have no idea what Seachem basis their Prime nitrate claim on, and I suspect it is inaccurate. Nitrate is pretty resistant to most types of chemistry, hence the reason a nitrate kit needs a special reducing agent to reduce it to nitrite before detecting it.

Randy, are you aware of any alternative data, or do you have any personal experience, that followed precisely the same testing controls and procedures as detailed in the experiment carried out by Tiffani Furlough or Kevin A. Senkevech, in the Fritz Ind Patent abstract "process for reducing the concentration of chloramines, chlorine, ammonia, nitrates and nitrites in saline and fresh waters by adding to the water a treating material selected from alkali metal and alkaline earth metal formaldehydesulfoxylates in a dry or solution form".

The water soluble, sulfur-containing, organic compound is represented by the general structural formula, Ra-A-Rb (Formula 1) wherein R is an anion having the formula —(OOS—CH2—OH) and A is an alkali metal or an alkaline earth metal. When A is an alkaline earth metal, then the integers a and b are 1. When A is an alkali metal, then a is 1 and b is 0. Sodium and potassium are preferred alkali metals and calcium and magnesium are preferred alkaline earth metals. The preferred treating material is sodium formaldehydesulfoxylate, which is sometimes referred to herein as SFS. The anion R, —(OOS—CH2—OH), is sometimes referred to herein as the FS anion.

"Thus, in accordance with the above postulated theoretical reaction mechanisms, it can be calculated that a single formaldehydesulfoxylate (FS) anion, R, of the treating material of this invention (95.10 weight units) reacts with 17.03 weight units of ammonia, 52.47 weight units of hypochlorus acid, 51.45 weight units of a hypochlorite ion, 51.48 weight units of monochloramine, 85.92 weight units of dichloramine 62 weight units of nitrate ion and 46 weight units of nitrite ion."

On either the Seachem product or Kordons most recent product Amaquel +?

If so, do you have any knowledge of the same results (suggestion of lower NO2 and NO3 levels in a controlled sample) been either replicated conclusivey, Inconclusivey or negative.

Thanks Tony.

 

[Randy Holmes-Farley]

Randy, are you aware of any alternative data, or do you have any personal experience, that followed precisely the same testing controls and procedures as detailed in the experiment carried out by Tiffani Furlough or Kevin A. Senkevech, in the Fritz Ind Patent abstract "process for reducing the concentration of chloramines, chlorine, ammonia, nitrates and nitrites in saline and fresh waters by adding to the water a treating material selected from alkali metal and alkaline earth metal formaldehydesulfoxylates in a dry or solution form".

The water soluble, sulfur-containing, organic compound is represented by the general structural formula, Ra-A-Rb (Formula 1) wherein R is an anion having the formula —(OOS—CH2—OH) and A is an alkali metal or an alkaline earth metal. When A is an alkaline earth metal, then the integers a and b are 1. When A is an alkali metal, then a is 1 and b is 0. Sodium and potassium are preferred alkali metals and calcium and magnesium are preferred alkaline earth metals. The preferred treating material is sodium formaldehydesulfoxylate, which is sometimes referred to herein as SFS. The anion R, —(OOS—CH2—OH), is sometimes referred to herein as the FS anion.

"Thus, in accordance with the above postulated theoretical reaction mechanisms, it can be calculated that a single formaldehydesulfoxylate (FS) anion, R, of the treating material of this invention (95.10 weight units) reacts with 17.03 weight units of ammonia, 52.47 weight units of hypochlorus acid, 51.45 weight units of a hypochlorite ion, 51.48 weight units of monochloramine, 85.92 weight units of dichloramine 62 weight units of nitrate ion and 46 weight units of nitrite ion."

On either the Seachem product or Kordons most recent product Amaquel +?

If so, do you have any knowledge of the same results (suggestion of lower NO2 and NO3 levels in a controlled sample) been either replicated conclusivey, Inconclusivey or negative.

Thanks Tony.

No. I have never seen any data that says one way or the other whether Prime detoxifies nitrate, but I am fairly confident it cannot.

 

[Malcontent]

Kuhns told me, via Facebook, that nitrite wasn't reactive enough (except at extreme pHs), and that the nitrite binding claims were likely false.

One of these days I'll design an experiment to test these detoxification claims.

 

[Tony Thompson]

My reference to the patent by John Kuhns (1985) was to show historical data of products which are currently in use based around the application of Formaldehyde bisulfite. The companies who supplied these products, including ARG and John Kuhns himself make no claims around the reduction in NO2 or N03-. The analysis and procedures did not target or as far as I can see, test for either of these particular polyatomic ions.

However the newer products, similarly based around Formaldehydebisulfite, for which the patent proceeds J Kuhns (Fritz 2006) detailed there testing procedures and measurement that did include bot N02 and N03-

If their is doubt surrounding the claims or testing procedures of Tiffani Furlough and Kevin A. Senkevech then I think it only fair and much more productive to ask them the questions.

Having no qualification or detailed understanding of chemical processes, I hoped that someone more qualified than myself could analyse the processes and data produced by Furlough and Senkevech in the experiments detailed by the link to the document I provided https://patents.justia.com/patent/7097773 and if they find any discrepancies in their procedure or controls progress the matter further by annotation or if possible by approaching Frtiz Industries. http://fritzind.com/

Just as a point of relevance, @Malcontent , rather than carrying out your own set of procedures, would it not be more valuable to first carry out the experiment using the same procedure as Furlough and Senkevech. I would think the first test should be to try and replicate the same results as claimed using the same controls.

Fritz Ind are a significant Chemical company that I would imagine have a professional set of testing and laboratory equipment at there disposal.

The patent and claims made on behalf of Fritz Ind are a completely new patent claim and therefore should not in my opinion be judged on a completely different (preceded) patent claim by John Kuhns.

For there to be a separate (proceeded) patent claim based around Formaldehyde bisulfite, or its synonyms. Then I would suspect that there are some variations that come into play.

If I may also make it clear that I have no bias one way or another regarding any of these claims, nor do I see an application where I would find it useful for the reduction of NO2 or NO3 in marine aquarium husbandry.

 

[Tony Thompson]

As a form of balance I would like to include this link to a claim that product claims of detoxifying NH3 may also be disputed.

5.5.3.1. Ammonia Detoxifying Chemicals in the Aquarium

There are no chemicals which can even temporarily "detoxify" ammonia in the aquarium.

aquariumscience.org

 

[Tony Thompson]

Extracted from Aquarium Science Website

"It is important to remember that it is perfectly legal for the marketing departments to make any claim they want to make with reference to any product as long as the product is not a human, cat or dog medication or food. We’ve even seen some “papers” put out by a “PhD” which had a very convincing blend of accurate science with science fiction. They were more hype. This is not a regulated industry! And the profit motive is a very strong motive." (aquariumscience.org)

 

[Dan_P]

Amquel (manufactured by Kordon)
along with the other product mentioned in your article
ClorAm X (manufacturerd by AquaScience Research Group)
state that both products contain HOCH2SO3Na. Neither of these products are stated by the relative manufacturers to "detoxify" Nitrite or Nitrate.

Although the more recent product by Kordon, Amaquel + (Amquel plus) also states to "detoxify" other Nitrogen Polyatomic Ions such as NO2- and NO3-.

The manufacturer Kordon states below:"

• Detoxifies ammonia including the ammonia found in chloramine
• Detoxifies chlorine including the chlorine in chloramine
• Detoxifies all of the kinds of toxic nitrogen compounds in the water
• Detoxifies all forms of ammonia/ammonium
• Detoxifies all forms of nitrites/nitrates
• Detoxifies toxic pheromones
• Does not affect the water's pH (acidity/basicity)
• Does not interfere with the beneficial nitrifying bacteria or their food sources
• Made in U.S.A.

Unfortunately unlike their original product 'Amaquel', the manufacturer does not give a statement of what the new product 'Amaquel+ contains. This however is a direct link in statements between both Seachem and Kordon on both of their products.

Interestingly, to me at least

I inadvertently wondered into this topic when I used the Seneye device to observe ammonia reduction/detoxification with Prime. I did the experiment twice because of the unexpected results. I started a discussion with Seachem and will conduct additional experiments using Seachem’s ammonia badge. @taricha is also very kindly conducting a few experiments. At the point that I feel discussions with Seachem tech support have hit a brick wall, I will share the lab results. The claim the Prime and other products detoxify nitrite and nitrate are too over the top to even debate.