Understanding Vibrant: Algaefix, Polixetonium Chloride / Busan 77

Dennis Cartier

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Nope, I responded to that. You just somehow missed my comment. Once again, I'd like to remind you that the spectra presented here are from unknown mixtures. Mixtures. Not pure compound like the reference spectrum supplied by Randy. Mixtures. Which, again, is what I have repeatedly asked about.
I saw your response, but did not view it as responding to the vast differences in the NMR's that Randy was pointing out. So no I did not miss your comment.
 

reef_ranch

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As I've stated repeatedly: I have no connection to UWC. The fact that you're so fixated on me rather than the substance of what I have to say is pretty concerning, friend.

I had my hypothesis somewhat formulated before I got here. I made the account to ask questions that were relevant to me determining its feasibility since not a soul here had actually questioned anything that was posted and the methodology was not entirely transparent. Major red flag to accept it all at face value considering the accusations associated with it. It actually requires minimal time and effort to find soft spots in the analyses here due to the approach that was taken.

Odd that you're criticizing me and not the people who have dedicated so much of their time and resources to performing all of these assays. Love the double standards here.
That doesn’t do it for me. Too much effort put into this for someone completely disinterested. Whether you put the effort in before or after you got here.
As I said, I not a scientist. I here to learn how best to keep my reef. If you have something constructive to add, I’ll learn. But I’ll have to rely on the other scientists to make heads or tails of what you offer.
But at the end of the day, you are not a disinterested contrarian. That much is clear.
 

jcolliii

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13cNMR.JPG

Look at the peaks in the 13C NMR on p1.
 
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Acalin

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Wow! Just wow!
Sorry, I tried extremely hard to hold back and not comment because what you guys are talking here is way above my knowledge.
BUT....
Seems like we are all on the wrong forum...
Maybe we should be on reddit? Make it easier for more people to chime in? Looks like there is a potential bigger pool of experts there than we have here.
Yeah, I know... I'm working on my sarcasm....

What are the odds of one guy, coming from another forum and knowing what to ask and dispute on in such a detail?

Maybe I dont' know what I'm talking about, but I sure do know what I am not going to buy nor recommend to others!

For those specific users who will be coming after me, I'll say this:
I didn't acuse anybody of anything. Just asked a statistical question.
To support my question, if you are coming to argue my post, please answer this first:
How comes that whenever I type a salwater aquarium related question on Google, I never get a search result that takes me to reddit? (At least not on the first or second page of my search - usually I find what I need in the first 2 pages).

I formed my opinion based on what I've seen and read here. Everyone had their chance to come up with some arguments and proofs. Some came with more evidence than others! (Sorry for the later ones, but life is vibrant! ;) ).

Honesty is all that is left at this point. That is paramount for me as I am sure it is for the vast majority of people here.
Only when you are honest you should attempt to start repairs.
 
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Dan_P

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Very interesting


Anyone else picking up on the very subtle but super obvious nuances in style of posting between this author and another poster here? Or don't?

Also can you post a link to subreddit thread that first directed you here?
I did notice MnFish1 hasn’t been posting :)
 

Dan_P

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Avidhexgrammid says "I don't really understand why the metabolite line of questioning hasn't been given adequate consideration throughout this. People keep saying it's impossible but nobody has actually said why and none of the assays were really designed to test it using deductive reasoning."

Response: There has been no line of questioning of metabolites. Quaternary ammonium compounds do not have ionizable groups since they are always charged and their NMR is largely pH independent.

Avidhexgrammid says "After some looking, it seems reasonable that something like cyanophycin synthetase and the colinium cation could work and still explain the quat aspect of things."

Response: Please provide your references and/or sources. After some looking, your suggestions do not seem reasonable. Cyanophycin synthetase is an enzyme that makes cyanophycin. Cyanophycin is a biobiopolymer, which is insoluble at physiological pH and ionic strength, has a high polydispersity with a molecular weight range of 60,000-100,000 Da, so cannot be the same compound isolated from Vibrant (ref: Biomacromolecules 2004, 5, 1166-1176). Moreover, the 1H NMR is completely different (ref: Biochim Biophys Acta 2001 Apr 3;1526(1):5-9). What is the "colonium cation"?

Please try to address the data presented rather than gaslighting.
…and don’t forget about “cherry picking” data.

”Gaslighting” is what a lawyer would use which coincides with the purpose of their entire exercise, swaying the jury.
 

Theawkwarding

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The purpose of this post is to look closely at Vibrant to compare its properties to a known algaecide, Algaefix by API. This is intended to shed light on the active ingredients in Vibrant, explain its mechanism of action, and give people insight into its use and what to expect. It is not a recommendation to use or not use either product. (apologies, I'm not a chemist and I hope inaccuracies in my descriptions aren't too distracting.)

Background on Algaefix / polixetonium chloride
Algaefix by API contains 4.5% “dimethyliminoethylene dichloride, ethoxylate” CAS 31512-74-0 per MSDS and EPA documentation. This amount is the same in the various Algaefix Marine, Pond, etc labels. This chemical is a polymeric quaternary ammonium compound. Other quaternary ammonium compounds or “quats” (not polymers), such as benzalkonium chloride are in widespread use as sanitizers, antibacterial soaps etc. The Algaefix chemical is also known by the trade name Busan 77 or the more recently EPA-favored name polixetonium chloride, I will refer to it by these or simply “the polyquat.”
Polixetonium chloride is a well-known algaecide, registered in the U.S. since 1971. The EPA documentation on it is thorough and has a number of useful bits of info. This 65 page EPA draft risk assessment from 2020 covers most relevant info, including the material below. This chart shows the concentrations at which it was found to have an inhibitory effect on various “algae”.

NwSAslRbmC9iOhq-EFOn_x4tGxmEM2vSMN5nP2FdUdprL_9JoKoyPxQHEch-w4b0jg2hLRwJd6yf0PjMNYXha5Hd7SIVifh-EB-cYWKTELn6ymJKRsVcVQ9FKAR-II7s7I-dIHkb

904MYe40dlobzLdhoec8IyOQugFE7IHKBSdk8ZgcNxDXLrkXsTA__nOKU4QVYlgQ9f9rxQLc6Vj7CFlmadRBpWHUm3HrW5imZef6FeJeK2_m_8Ez8ZzOpMu2iEFSI9iAuJxUTI_w


The approximate concentrations for each group are: diatoms and cyano at ~0.1ppm, green algae at ~0.01ppm, and vascular plants at ~1ppm. The label dose of Algaefix results in an addition of ~1ppm per every 3 days. Perhaps unexpectedly, it does not seem to leave the system (though it would be expected to dissipate from the water).
“Polixetonium chloride is miscible in water [study #’s…] and is not expected to degrade by either abiotic processes [...] or biotic processes [...] Sorption to soil, sediment, and sludge is expected to be the primary route of dissipation, based on the fact that polixetonium chloride is a quaternary ammonium compound that has a positive electrical charge.
A ready biodegradability study […] demonstrated stability to microbial degradation in a WWTP [wastewater treatment plant], which is consistent with the results of other non-WWTP microbial degradation. Therefore, for polixetonium chloride, there is no apparent route of chemical or microbial degradation.”

One final note on known properties and uses of polixetonium chloride is that this same chemical(nih.gov) under the name Bubond 60 is also used as a coagulant / flocculant. This helps shed light on reports of increased water clarity with aquarium usage of the product.

A paper shared by @jeffww illustrated the use of a distinctive Bromphenol Blue color response (non-pH) to detect quats dried on surfaces. I noted a quat-like color change with both Algaefix and Vibrant, but in none of almost a dozen bottled bacteria hobby products or saltwater. After that, a more thorough investigation of Vibrant and Algaefix properties was undertaken. Below is the first part of those results.


Part 1: Professional Lab Tests indicate indistinguishable principle ingredients in Vibrant and Algaefix - polixetonium chloride
Samples of Algaefix and Vibrant were poured from the product bottles into labeled 50mL centrifuge tubes and shipped to a lab for NMR testing. 1mL of each was vacuum-dried and the residue taken up in heavy water for analysis by 13C and 1H NMR. A separate partially-used bottle of Vibrant was sent to @jeffww for FTIR comparison to Algaefix in another lab. Those samples were also dried under vacuum for FTIR analysis.

A) 13C NMR
This is a test that generates a magnetic resonance response from Carbon atoms in the sample. The resonance refers to the frequency at which certain carbon atoms will oscillate when pushed around by magnetic fields. Their preferred frequency depends on their local environment - that is, what they are bonded to. Thus a 13C NMR is a probe of the chemical structure of the compounds, with each Carbon atom in the compound being shifted to a different place in the graph by what it is bonded to. More thorough intro for 13C NMR in this text, and a follow-up.
C16dHaUioEVk0GbjL5HbuqAtq1uZg1CAwdd0PDtFVcsgfheBBnMFEIBuDVV6IIYG8wI2C6D9-QK8sFrErsa8Ki8wAbjgjKLyvu_ki-jtHxtjSFgf_XqW4OohDh0qvyGvjIZqpz28

In the above graph you can see that the samples of Algaefix and Vibrant possess only Carbon in the same bond environments as each other, and the Carbon atoms are in those environments in the same ratios.

A wider view shows the blank around 170 ppm chemical shift where aspartic acid (and any other amino acid) would have a peak, if there were any in the samples.
gBzbrg2n4HHqpKJZUBpI_PrW4zz85EAXTBTXYEmzV_-2BJ_Py5y8Tecbxg7BfZTXy_pnp3fI7DUjfH4FRKp95LwGC9uow1kjS-aNZN8jXok96ElC8pUAaaEj2P2_Ff3aA5Q4u9fZ



B) 1H NMR
This is the same process described above but for Hydrogen instead of Carbon. In the below data you can see that the hydrogen atoms in each sample also exist in the same bond environments and are in those particular environments in the same ratios.
fp6HDDZVlnqweOtJUOIzUQpTmjsKfS6stsoTfbZ-_EGtrh9LPU1-invwpYguiHKmaVdLjSUEswfkfhrYdmQ_nfouf3Hs98S1_9tgZg_PT006Yjf7YBS6_h7ZWxxnHG1OJOV6-pfq


Since both the Carbon and Hydrogen atoms are bonded in the same way in these vacuum-dried samples of AlgaeFix and Vibrant, this covers all possible organics in the residue.

C) FTIR
This process generates an absorption spectrum in the infrared region where chemical compounds are distinctive in what wavelengths they absorb.
uHsH1WBMlJgau3lOIZOhzgtk1yaehUtGXAxXjjz23thQ-UgBRuF0GftG8P7R3mSvZdLPlxLILlypWxGA0m9iJov3GTGMLFUVr2izE9eYyDLlbhdggOQg84JEizgRjY7R3oPZ-IKD

Again, the precise alignment of the absorption peaks and the consistency of their peak height ratios between the vacuum-dried samples of Algaefix and Vibrant tells us that the residues are the same compounds with no additions. (The addition of aspartic or other amino acids would be very obvious in this data as well).
In addition to being able to say that Algaefix and Vibrant contain only the same compounds in their dried residues, we can further compare that to a given FTIR spectrum for polixetonium chloride “Busan 77” (posted online).
yz9cA8UWj_-VzdeBJne4R_OWNFmCF9JJaBK2heOYlGg_RS9QYzxDSCdPzSEy7uNLSpHuoOBZB6xDHxNPmp1QblO8l5FlA10a88uRqfv6W06eAb7v7oTUYl50FcoEM3LoHrdh-90O

This level of agreement confirms further that what was measured by the above tests in samples of Vibrant and Algaefix is indeed the polyquat that is the well-documented label ingredient in Algaefix, polixetonium chloride.

next...
Part 2: quantification / comparison of the amount of polyquat in Vibrant and Algaefix

edit: 2/28/22
Part 2: post 16 here
Part 3: post 165 here

UWC response 2/28

edit: 3/10/22
Sample NMR test replication was done by @jda (so different hobbyist, different bottle from a different source, sent to a different lab with different technicians.) Results (1H NMR) he received are in post 731 here
 

rmorris_14

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That's the problem.

Alrighty.

I already provided a multitude of sources formatted as hyperlinks in a previous comment. Reef tanks aren't maintained at physiological pH, but okay. I don't understand how it's so preposterous that the proenzyme could be maintained in the bottle and become activated by potassium and magnesium ions in tank water. Cyanophycin is a suggested pathway for nitrogen uptake, I'm not saying it's correct, I'm saying it's feasible and that you guys have neglected to consider (and rule out) practical alternatives to your conspiracy theory because of how you've framed your hypotheses. Choline seems to be a much more compelling argument anyway with the data that's been collected here.


I don't see how what I've said could be perceived as gaslighting. I'm suggesting an alternative hypothesis, not making anyone question their own reality. If anyone here is somehow questioning their reality because of something I've said, then they probably didn't have a firm grasp on it to begin with.

As indicated previously: choline is a naturally produced QAC that has lytic properties on algal cell walls. Since you guys seem to prefer to observe similarities instead of considering potential differences, let's gaze upon an FT-IR spectrum of choline chloride from this paper. Shall we superimpose it with that of Vibrant? Shall we acknowledge the subtle changes that occur when it's mixed with another compound and the concentration is varied? Shall we recall that all analyses presented here have been for mixtures, not pure compounds?
FT-IR-spectra-of-choline-chloride-ChCl1-2-propanediol-12-and-ChCl1-2-propanediol.png
When all else fails, throw out words like “conspiracy theory”
 

moz71

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Looks like a duck, walks like a duck, quacks like a duck, Nope It still could be a rabbit! Lol
 

Theawkwarding

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Is there an introduction to this on another thread.
Why do we jump in to comparing Vibrant with Api and luckily finding that they are the same.
Why is it that just Api and vibrant have been compared and NO other product on the market.
The data is conclusive if the study has been done correctly but without the information of what has lead to the study and just comparing one product to another makes things a little bit suspicious.
 

shwareefer

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Odd that you're criticizing me and not the people who have dedicated so much of their time and resources to performing all of these assays. Love the double standards here.
Really? You can't see why that might happen? People with a proven history and who have "dedicated so much of their time and resources to performing all of these assays" being trusted more than an interloper. You are right it's bizarre.

avidhexagrammid = DrZoidburg. Will say anything except the results might be correct.
 

atoll

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Would I use vibrant in my reef? Nope. Would I use it in a fish only system possibly.
Everything in between is supporting an argument either way. Decision made, end of.
 

ingchr1

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As I've stated repeatedly: I have no connection to UWC. The fact that you're so fixated on me rather than the substance of what I have to say is pretty concerning, friend.

I had my hypothesis somewhat formulated before I got here....
A couple of questions that may help:
  • What lead to you forming a hypothesis? Since you have no connection to UWC, is Vibrant a product that you used on your tank and thus had concern?
  • No identifying details, but in general what are your credentials?
  • What type of tank do you keep? Can you post up a photo so we can see what you have?
 

shwareefer

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Is there an introduction to this on another thread.
Why do we jump in to comparing Vibrant with Api and luckily finding that they are the same.
Why is it that just Api and vibrant have been compared and NO other product on the market.
The data is conclusive if the study has been done correctly but without the information of what has lead to the study and just comparing one product to another makes things a little bit suspicious.
There is honestly so much history on this. No offence but no one has jumped the gun except maybe you.

jda was sounding the alarm since 2019.


ScottB had an honest question.


That led to the thread we are in, which you didn't read, and this one.

 

jda

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Seriously, just ignore these folks. If they put some skin the game, then response can be due and it will come from one of the experts that are on this thread. Otherwise, you are giving them just what they want, which is a place to sow doubt, twist the narrative and otherwise modify the engagement.

If one of them has a build thread, or even a post outside of this topic... then maybe.

If any admin does not know how to look for users with duplicate IPs, let me know. The software used to have a feature, but you can also grep the logs.
 

shwareefer

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Seriously, just ignore these folks. If they put some skin the game, then response can be due and it will come from one of the experts that are on this thread. Otherwise, you are giving them just what they want, which is a place to sow doubt, twist the narrative and otherwise modify the engagement.

If one of them has a build thread, or even a post outside of this topic... then maybe.

If any admin does not know how to look for users with duplicate IPs, let me know. The software used to have a feature, but you can also grep the logs.
Right. Too much coffee today.
 

jcolliii

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Very interesting


Anyone else picking up on the very subtle but super obvious nuances in style of posting between this author and another poster here? Or don't?

Also can you post a link to subreddit thread that first directed you here?
Dunno... Hexagrammidae is a family of marine fishes. Avid perhaps implies a researcher or collector of greenlin fishes?
 

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