Understanding Vibrant: Algaefix, Polixetonium Chloride / Busan 77

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
New to the "Vibrant scandal" is this the actual "scientific study" or does someone have a link to it as there is a lot missing to fulfill the bas
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.

Its quite a simple question as all I could find was other peoples experiences and not the researchers.

My "expertise" is in misinformation within experiential learning, it was my dissertation subject within my PostGrad.
I have learnt to not jump on something that hits me emotionally and instead ask why.

Yes I have used Vibrant did I have any negative impacts from it? no. Would I use it again? no because I couldn't say the outcome was worth the money.

I know the back story behind vibrant and all the anecdotal data, but not the background around this study which is why I asked. I'm not going to just believe something someone I don't know posts on a forum without having all the facts behind the research. I've seen research that shows Broccoli having a higher protein value than beef but the data was twisted to fit the narrative of the researcher so what they were saying was technically correct it was heavily misrepresented.

If anything I'm encouraging to fill the holes within the study to make it more reliable.

Its important that all the information is available. If someone you didn't know released a personal study saying that Vibrant was also the same as something like Microbacter 7 but only posted the results and conclusion because the rest of it is somewhere else would you not stop and question what's going on before drawing judgment??

I'm neither for nor against the study, I just want to make a reliable educated judgment moving forward because instead of buying vibrant I could just buy algae fix.

And if you want to know if I'm a real person and not connected to Vibrant just look up my Insta, Yorkie_Reefer.
 

jcolliii

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Have you read through all of the pages of this and the thread on Vibrant in the SPS section of this forum? If so, instead of casting a general aspersion, why not ask specific questions that have not already been addressed? For example, what do you see as holes?
 

Theawkwarding

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Have you read through all of the pages of this and the thread on Vibrant in the SPS section of this forum? If so, instead of casting a general aspersion, why not ask specific questions that have not already been addressed? For example, what do you see as holes?
Like many, I have read many posts on this thread but can not say I have read them all but this is my point.

If you read my original post and the one after it mentions the holes and issues.

"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."

I simply asked for where the missing information was and explained why I found it suspicious.

A simple introduction would mean that people who have not read every post on Reef2Reef would be able to see why this study has been done in the way it has. Isn't Reef2Reef supposed to be open to all in the hobby new and old? How would someone new know where to start from just reading this research?

It could be as simple as.

Due to an ever increasing amount of negative experiences for reef hobbyists using Vibrant there has been an increased suspicion that Vibrant Aquarium Cleaner does not contain the ingredients it says it does. An article on Reef2Reef by ScottB https://www.reef2reef.com/threads/my-speculation-vibrant-has-some-fluconazole-in-it.867114/ suggests that Vibrant contains the same chemicals as another well known algicide by API. This study was designed to to test the theory that Vibrant has the same ingredients as API Algae Fix.

Its a simple thing that casts aside many questions that can lead to doubt about a study.
 

jcolliii

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This is given - the context, the reasons, etc., methodologies. You just have to go do the legwork of reading it. The threads are linked. Other products tested. It's all there.
 

rtparty

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Like many, I have read many posts on this thread but can not say I have read them all but this is my point.

If you read my original post and the one after it mentions the holes and issues.

"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."

I simply asked for where the missing information was and explained why I found it suspicious.

A simple introduction would mean that people who have not read every post on Reef2Reef would be able to see why this study has been done in the way it has. Isn't Reef2Reef supposed to be open to all in the hobby new and old? How would someone new know where to start from just reading this research?

It could be as simple as.

Due to an ever increasing amount of negative experiences for reef hobbyists using Vibrant there has been an increased suspicion that Vibrant Aquarium Cleaner does not contain the ingredients it says it does. An article on Reef2Reef by ScottB https://www.reef2reef.com/threads/my-speculation-vibrant-has-some-fluconazole-in-it.867114/ suggests that Vibrant contains the same chemicals as another well known algicide by API. This study was designed to to test the theory that Vibrant has the same ingredients as API Algae Fix.

Its a simple thing that casts aside many questions that can lead to doubt about a study.

Multiple other products were tested. Some with the same active ingredient and others that are known bacterial additives.

It's all in the posts from Taricha. They do span a couple pages. I really wish an admin would edit all the posts into the first post if they can
 

Malcontent

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All these new, low post count accounts are highly suspicious. The usual strategy is to create the appearance of controversy where none actually exists. It's hard to do this with a single account so it's important that they get a few more accounts to agree with them.
 

Dan_P

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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.
Have you started reading this post at #1? Go through it skipping all the replies. Stick to @taricha posts first, then go back and read what everyone else thinks. It is a good way to understand what was been done and what the subplots are in this story.

Vibrant has a long history of being suspected of not being what it says it is. Also, the product like many products, has questionable claims. Early investigations indicated it was an algicide, but the data was not widely shared. Recently, @taricha and others upped their game, obtaining evermore sophisticated analyses of Vibrant. The results were amazingly clear: Vibrant samples gave the same analytical profile as a popular algicide.

The science and analytical work behind this investigation are sound and repeatable. Is it an open and shut case? In science, it never is. The data is very compelling though. It might need further confirmation if it were to be used to support legal or business matters. To put things in perspective, in a patent infringement case, this data would probably be strong enough to cause the lawyers on both sides to huddle together to work out a compromise.

Good luck with your reading assignment :)
 

jcolliii

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All these new, low post count accounts are highly suspicious. The usual strategy is to create the appearance of controversy where none actually exists. It's hard to do this with a single account so it's important that they get a few more accounts to agree with them.

Yep. I see the same trend.

Anyone ever read Merchants of Doubt? I think you might still be able to see in on Youtube. Absolutely fantastic expose on how big tobacco and the anti-global change lobby have influenced opinion through repeated untruths, partial truths, and by putting forward your own 'experts' who talk loudly enough and long enough that folks who come into the conversation late, or those already likely to want to see a specific conclusion (perhaps one not supported by data) can see the answer that they want.
 

revhtree

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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.
Thank you.

We do know how and trust me when I say we use the tools we have to make sure people are not shilling here or any other areas. It’s not perfect but we do what we can do.

If we were to find something we would address it.
 

avidhexagrammid

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13cNMR.JPG

Look at the peaks in the 13C NMR on p1.
Slow down there, buckaroo. The sources I posted on choline-based ionic liquids indicate it's usually bonded to another molecule. The number of peaks is dependent on the structure of the compound and there are a multitude of possibilities. The point is that it is something that would produce signals in the same chemical shift range as polixetonium because it's a quaternary amine. But hey, while you're at it, can you characterize polixetonium from the sample spectra?
 

avidhexagrammid

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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.
I'm not really interested in what does or doesn't do it for you, I don't owe you an explanation about who I am. Keep in mind that what you might perceive as too much effort is something that could be relatively simple for someone else. Some weird assumptions there, but they're yours to nurture I guess.

…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.
You're free to dissect my comments and point out where I've misled you and caused you to question your reality using sinister means. Or perhaps it's time to lay off with this garbage and attack the my arguments instead of me. These dog-piling antics are counterproductive and, again, really just illustrate a pervasive lack of objectivity.

When all else fails, throw out words like “conspiracy theory”
Nah, by definition, that's what it is. There have also been a variety of self declarations throughout this thread before I made my comment. Can I help you with anything else?

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.
Make no mistake, the amount of time I spent doing a basic lit review is incredibly pale compared to the time and money spent doing these assays. So yeah, it's a pretty flimsy double standard.
 

a.t.t.r

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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.
Because you missed the older threads where it was originally compared to flux
 

rtparty

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So let's pretend Vibrant is choline (or whatever it would be called to be in the form UWC...I mean avid...is claiming) just for giggles.

Does the label match this in any way?

Vibrant Ingredients:
  • 95% Cultured Bacteria Blend.
  • 1% Amino Acids (Aspartic Acid)
  • 0.5% Vinegar.
  • 3.5% RO/DI Water.
 

Courtney Aldrich

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Slow down there, buckaroo. The sources I posted on choline-based ionic liquids indicate it's usually bonded to another molecule. The number of peaks is dependent on the structure of the compound and there are a multitude of possibilities. The point is that it is something that would produce signals in the same chemical shift range as polixetonium because it's a quaternary amine. But hey, while you're at it, can you characterize polixetonium from the sample spectra?
Choline-based ionic liquids do not have any useful algaecidal activity for aquaria. The papers you mentioned (https://doi.org/10.1016/j.seppur.2020.117288) use 50% by weight of the choline ionic liquids to kill algae. Now, that is a lot choline! For a 100 gallon aquarium, this would require about 50 gallons of your choline ionic liquids, which would kill everything.

The NMR spectra of choline are very simple and do not match the NMR from Vibrant. Yes, choline has a counteranion to balance the charge in the ionic liquid. The paper you cite uses diphenylalanine, which would give up to 14 additional carbon signals. As you can see, the 13C NMR spectra of Vibrant has 4 large signals with peaks with peaks at 52, 57, 64 and 65 ppm that correspond almost precisely with the predicted chemical shifts of polixetonium chloride (ChemDraw version 20.1 from Perkin Elmer). Moreover, the peak size of the chemical shift at 52 ppm corresponds to the 4 methyl groups and is predicted to be about twice the intensity of the other carbon peaks (that each represent 2 carbons). As you can from the NMR on the first post, the peak at 52 ppm is about twice the size of the other peaks. Taken together with the 1H NMR and IR data, I think the data is pretty compelling. The NMR has been independently confirmed by another member as well.

Polixetonium chloride NMR.jpeg
 
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ScottB

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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.
Yes, linked below is the precursor thread. All of the popular "Bacteria" products were run through the bromophenol blue (BPB) indicator process. In only two of the products was the presence of quaternary ammonia detected. Vibrant and AlgaeFix.


 

Sean Clark

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While still having the "BRS Recommended" badge on it.
Screen Shot 2022-02-25 at 7.20.28 PM.png


Like they're still recommending it, just it happen to run out of stock at the moment.
It appears that the BRS recommended badge is gone now. I am not sure when this happened but it did :)
 

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