Understanding Vibrant: Algaefix, Polixetonium Chloride / Busan 77

[Randy Holmes-Farley]

They could have not only bound the QAC directly, but also ate algae with the QAC bound?

That's an interesting point. Organisms that eat materials that could have complexed vibrant might get more into them than from simple water exposure, and exposure to the contents of the GI tract might digest away some of the nonvibrant parts of a complex.

That might even relate to filter feeders like clams, and could be an effect that builds over repeated doses even if the aquarium water is not rising in concentration. The stuff being eaten may get more and more saturated with the polymer.

 

[jda]

For those who have not owned clams, they filter a massive amount of water... massive. Assuming that waterborne stuff (protozoa, bacteria, algae, whatever) get met with the QAC first and at full concentration, there is probably plenty if it to get filtered by the clams.

 

[LRT]

All I know is my clams and oysters are the first critters to alert me when my water quality is off. Ive lost a couple over the years just letting my rodi get away from me! I could not imagine what would happen if I dumped a mulloscicde on them.

 

[Dan_P]

To be clear, my interpretation is that when it goes in to the tank, it's in its most potent form - not bound to anything, and very different than when I detect it later.
When I measure vibrant-associated-material a week or two later, it's got to have found some stuff to attach to. Thus it would be much less potent - if at all.

I'd dismiss this water-lingering material entirely if it weren't for the fact that when I did week after week of algaefix every 3 days, I stopped once I noticed effects on shrimp. Then over the next few weeks I saw multiple other classes of inverts react poorly. (doesn't exclude the possibility it was just the accumulated effect from weeks of additions, and maybe the lingering material in the water didn't actually bother inverts)

Good to know. I am planning an experiment to use Ulva nutrient uptake to test its potency over time.

 

[blaxsun]

Response will be delayed. Jeff (owner of UWC) intended to respond yesterday, but the EPA and Mn Department of Agriculture arrived at UWC yesterday for a "for cause" inspection. I am told they were there all day yesterday and plan to be there again today.

FWIW, I saw a picture of the first page of the official EPA notice as proof.

And the plot thickens...

 

[jeffww]

Semi-related but I lost my algae eating farlowella in my planted tank by using algaefix in it as an experiment a few months back. Only death I experienced using the product. Was a risk and a lesson learned.

 

[taricha]

That's an interesting point. Organisms that eat materials that could have complexed vibrant might get more into them than from simple water exposure, and exposure to the contents of the GI tract might digest away some of the nonvibrant parts of a complex.

That might even relate to filter feeders like clams, and could be an effect that builds over repeated doses even if the aquarium water is not rising in concentration. The stuff being eaten may get more and more saturated with the polymer.

was reading this relevant bit the other day. It seems a plausible mechanism for what might happen to saltwater clams.
But a large clam pushing a big volume of polyquat-treated water across its gills could be just as good a mechanism for harm as the ingestion of bound particles.

"Neutral particles that encapsulate the biocides with nutrients may be a solution when ingested by filter feeders which is a predominant form of feeding among biofouling organisms. The principle is that the particles, in the size range of 40 to 250 μm, are identified as food by the filter feeder and are taken up and concentrated in the organism, whereupon the biocide is released and kills the organism. ... Costa et al. (2012) published data showing the effectiveness of particles which incorporated polyquat biocide on zebra mussels.

...Costa et al. (2012) discussed this further and indicated that freshwater and saltwater mussel species (e.g., the blue mussel, Mytilus edulis), and other species of suspension feeders (e.g., sea squirts, sponges and bryozoans) would be susceptible to a neutral particle strategy, but research would be needed to define the best biocide cores and nutrient shells to target the species of interest."

-Review of in-water hull encapsulation and enclosure treatments for eliminating marine biofouling...

And here's another full paper...
Microcapsulated biocides for the targeted control of invasive bivalves

"Laboratory exposures demonstrated that two formulations effectively controlled the Gulf wedge clam Rangia cuneata, an IAS currently spreading rapidly through Europe. A single dose of 2–6 mg L−1 of the active ingredient in a static system achieved 90% mortality after 30 days of exposure."

"In addition, independent assessment by regulatory authorities concluded that sufficient evidence exists to support the assumption that, following breakdown of BioBullets, the active ingredients of both SB1000 and SB2000 will sorb to organic material in water, such that aquatic phase concentrations should be negligible. The active ingredient in SB1000 is a cationic polymer that functions as a surfactant. Surfactants are toxic to bivalves because they adsorb at the plasma membrane, including gill tissues, disrupting transfer mechanisms between the cells and the surrounding medium and causing cytolosis."

 

[taricha]

I went hunting to see if I could track down the basis for the claim on Algaefix Marine labels.
"When used in saltwater aquariums, Marine AlgaeFix will not harm snails, clams, scallops, shrimp, anemones, sea cucumbers, feather dusters, coralline algae, soft corals, hard corals, and other invertebrates."

This statement is EPA-approved, but the EPA documentation on Polixetonium chloride (linked in 1st post) doesn't provide a basis for this.
And it seems a gray area - there are people who use it and find no harm (it's obviously less toxic than in freshwater), but there are others who find it probably did cause harm to inverts in saltwater under some circumstances. (my observed losses with heavy algaefix: 4 out of 4 peppermint shrimp, 4/5 urchins, 2/2 turbo snails, 1/1 montipora, 1/1 sand sifting cucumber, 2/~dozen hitchhiker bivalves)

I found this interesting document from 2004 where EPA denies API's request to say it's safe for reef inverts.

"General Comments:
Toxicity Studies in Saltwater and Reef Aquaria

While the submitted data did indicate no mortality from treatment with AlgaeFix, several things make the study of questionable scientific validity. Given the concerns in the attached review, the Agency cannot draw any scientific conclusion from the submitted data. Aquatic studies submitted according to OPPTS Guideline requirements have provided sufficient data to characterize Busan 77 as highly toxic to freshwater organisms, ranging from highly toxic to slightly toxic to marine organisms. Since the concentration of the test chemical was not determined in the study submitted with this package, it is unknown whether the level achieved during application according to label directions will approach levels shown to be toxic to marine invertebrates in the Guideline studies. If you wish to be protective of aquarium organisms such as marine crustacea, further analyses of the concentration of Busan 77 in the water during treatment with AlgaeFix should be conducted to ascertain that it does not approach the levels shown to be toxic to marine invertebrate species in the submitted studies [Mysid, LC50=13ppm (95% confidence interval of 9.1 - 16ppm) NOEC < 7.8 ppm; Quahog clam, LC50 = 350 ppb (95% confidence interval of 0 - 710 ppb), NOEC =230 ppb. Data from published scientific literature may also provide toxicity endpoints for additional species of interest, some of which may be more sensitive than the species tested in EPA Guideline studies."

That was in 2004, but by 2007, apparently additional data had been submitted that satisfied EPA's concerns. The product label documentation in 2007 contains the familiar approved claim of saltwater safety for inverts.

I say that it must've been additional data, because the EPA still (in 2020) has basically the same low 48hr LC50 for quahog clams - 0.21mg/L.
It's unclear to be how the recommended dose of Algaefix being ~1ppm of active ingredient can square with that unless they showed data that must've said it bonds very quickly and disappears from the water.

Curious if anyone else has seen any data that sheds light on the degree of "safety" for this ingredient in saltwater.

 

[Dan_P]

I went hunting to see if I could track down the basis for the claim on Algaefix Marine labels.
"When used in saltwater aquariums, Marine AlgaeFix will not harm snails, clams, scallops, shrimp, anemones, sea cucumbers, feather dusters, coralline algae, soft corals, hard corals, and other invertebrates."

This statement is EPA-approved, but the EPA documentation on Polixetonium chloride (linked in 1st post) doesn't provide a basis for this.
And it seems a gray area - there are people who use it and find no harm (it's obviously less toxic than in freshwater), but there are others who find it probably did cause harm to inverts in saltwater under some circumstances. (my observed losses with heavy algaefix: 4 out of 4 peppermint shrimp, 4/5 urchins, 2/2 turbo snails, 1/1 montipora, 1/1 sand sifting cucumber, 2/~dozen hitchhiker bivalves)

I found this interesting document from 2004 where EPA denies API's request to say it's safe for reef inverts.

"General Comments:
Toxicity Studies in Saltwater and Reef Aquaria

While the submitted data did indicate no mortality from treatment with AlgaeFix, several things make the study of questionable scientific validity. Given the concerns in the attached review, the Agency cannot draw any scientific conclusion from the submitted data. Aquatic studies submitted according to OPPTS Guideline requirements have provided sufficient data to characterize Busan 77 as highly toxic to freshwater organisms, ranging from highly toxic to slightly toxic to marine organisms. Since the concentration of the test chemical was not determined in the study submitted with this package, it is unknown whether the level achieved during application according to label directions will approach levels shown to be toxic to marine invertebrates in the Guideline studies. If you wish to be protective of aquarium organisms such as marine crustacea, further analyses of the concentration of Busan 77 in the water during treatment with AlgaeFix should be conducted to ascertain that it does not approach the levels shown to be toxic to marine invertebrate species in the submitted studies [Mysid, LC50=13ppm (95% confidence interval of 9.1 - 16ppm) NOEC < 7.8 ppm; Quahog clam, LC50 = 350 ppb (95% confidence interval of 0 - 710 ppb), NOEC =230 ppb. Data from published scientific literature may also provide toxicity endpoints for additional species of interest, some of which may be more sensitive than the species tested in EPA Guideline studies."

That was in 2004, but by 2007, apparently additional data had been submitted that satisfied EPA's concerns. The product label documentation in 2007 contains the familiar approved claim of saltwater safety for inverts.

I say that it must've been additional data, because the EPA still (in 2020) has basically the same low 48hr LC50 for quahog clams - 0.21mg/L.
It's unclear to be how the recommended dose of Algaefix being ~1ppm of active ingredient can square with that unless they showed data that must've said it bonds very quickly and disappears from the water.

Curious if anyone else has seen any data that sheds light on the degree of "safety" for this ingredient in saltwater.

I am starting to collect observations that Randy suggested, Vibrant concentration changes when solutions are exposed to samples of aquarium contents, water, algae, sand, etc. Still collecting data and will do a data dump here.

There is one point I wonder about. For aquarists that suffer livestock loss, multiple additions were probably made. How much, how fast? As your aquarium experiment suggests, not all the dosed Vibrant is removed from solution. Why? Is there a limit to what an aquarium can remove or bind? This adds to the uncertainty of the concentration that causes problems. It also sggests that the algicide could be ineffective because of an insufficient concentration? For a 1:1 algae surface area to total aquarium biofilm surface area, how much is actually adhering to the algae target?

And finally, can the amount of polyquat concentration lost from solution be correlated to the surface area of biofilm? Is that number roughly fixed?

 

[blaxsun]

I haven't been able to keep any urchins for the past 6 months (tried 5 different attempts but they all died within a few days).

 

[taricha]

I am starting to collect observations that Randy suggested, Vibrant concentration changes when solutions are exposed to samples of aquarium contents, water, algae, sand, etc. Still collecting data and will do a data dump here.

Agreed. These will help fill in the picture a lot.

There is one point I wonder about. For aquarists that suffer livestock loss, multiple additions were probably made. How much, how fast? As your aquarium experiment suggests, not all the dosed Vibrant is removed from solution. Why?

For me it was maybe 15+ doses, mostly every 3 days. Recommended for algaefix. Seems accumulation in some form can't be ruled out.

 

[Randy Holmes-Farley]

In case anyone missed it in the now closed thread in the main forum, I'll repost this here:

As to next steps, REEF2REEF management has notified UWC that a suitable response is expected by a specific deadline in order to remain in good standing on this site. As of my writing this, they have not responded to that communication (which did not go through me) [this is still true as of this posting].
In my opinion, the logical place to respond is the science thread in the chem forum [that means this thread], so there’s no concern about this closed thread [meaning the other thread]preventing a response.
That thread is still open for any sort of science discussion of Vibrant and it’s composition, but not discussion of tangential topics.

 

[Dan_P]

Agreed. These will help fill in the picture a lot.


For me it was maybe 15+ doses, mostly every 3 days. Recommended for algaefix. Seems accumulation in some form can't be ruled out.

Hokey smokes! That seems like a bunch of Vibrant.

Your measurement of free Vibrant in the posted example suggests (maybe) accumulation could be large. Also, depending on where it is being adsorbed, say a biofilm, then might the biofilm become toxic to biofilm consumers or maybe toxic one or two trophic levels up?

 

[taricha]

Hokey smokes! That seems like a bunch of Vibrant.

Your measurement of free Vibrant in the posted example suggests (maybe) accumulation could be large. Also, depending on where it is being adsorbed, say a biofilm, then might the biofilm become toxic to biofilm consumers or maybe toxic one or two trophic levels up?

A bunch! And yet... GHA was still at problem levels on the rocks when I stopped (noticing I was missing shrimp).
That's part of why I think my organic-laden water reacted with the bulk of the algaefix before it hit surfaces.
It's complex to unravel. While one might think ingestion of algae/biofilm by grazers like urchins and turbos is a plausible path for toxicity, the peppermint shrimp do no such thing and also died. So maybe they all just got the expected pathway water-to-gills from dose after dose.

Either way, livestock die-off and GHA that sticks around is the worst of both worlds, hence my thinking that I'd run a bunch of GAC and clear water of organics before I considered using this chemical (slowly) again.

 

[Randy Holmes-Farley]

UWC has not responded, either publicly or privately.

Consequently, Reef2Reef has temporarily suspended UWC as sponsor pending further resolution of the situation

 

[Trickman2]

A bunch! And yet... GHA was still at problem levels on the rocks when I stopped (noticing I was missing shrimp).
That's part of why I think my organic-laden water reacted with the bulk of the algaefix before it hit surfaces.
It's complex to unravel. While one might think ingestion of algae/biofilm by grazers like urchins and turbos is a plausible path for toxicity, the peppermint shrimp do no such thing and also died. So maybe they all just got the expected pathway water-to-gills from dose after dose.

Either way, livestock die-off and GHA that sticks around is the worst of both worlds, hence my thinking that I'd run a bunch of GAC and clear water of organics before I considered using this chemical (slowly) again.

I have had urchins die off using Vibrant...Another interesting thing to think about is....Many people attack algae on a multi-front approach. So some may have dosed Algae-fix and Vibrant together. I wonder what the effect of doubling up on Busan 77 is? What is the concentration of Busan 77 is in Vibrant? I can't remember if I have ever done this but at some point I am sure I have had a bottle of both on the shelf.

 

[jeffww]

A bunch! And yet... GHA was still at problem levels on the rocks when I stopped (noticing I was missing shrimp).
That's part of why I think my organic-laden water reacted with the bulk of the algaefix before it hit surfaces.
It's complex to unravel. While one might think ingestion of algae/biofilm by grazers like urchins and turbos is a plausible path for toxicity, the peppermint shrimp do no such thing and also died. So maybe they all just got the expected pathway water-to-gills from dose after dose.

Either way, livestock die-off and GHA that sticks around is the worst of both worlds, hence my thinking that I'd run a bunch of GAC and clear water of organics before I considered using this chemical (slowly) again.

If shrimp eat busan 77 flocced detritus they might be susceptible to it.

 

[Dan_P]

I have had urchins die off using Vibrant...Another interesting thing to think about is....Many people attack algae on a multi-front approach. So some may have dosed Algae-fix and Vibrant together. I wonder what the effect of doubling up on Busan 77 is? What is the concentration of Busan 77 is in Vibrant? I can't remember if I have ever done this but at some point I am sure I have had a bottle of both on the shelf.

If you are not in a hurry, wait until I get you some data on what Vibrant “sticks” to in an aquarium and how that might be variable.

Also, I just started dosing Vibrant to several algae cultures. I am monitoring the health of the algae and Vibrant concentration. I might obtain some useful information for Vibrant users. It will take a couple weeks.

Dan

 

[ReefGeezer]

I suddenly lost a couple of Urchins (pincushion) and a Sea Hare while using Vibrant but still don't know if it was the cause. I was dosing IAW the manufacturer's directions.

 

[MnFish1]

Something from a science perspective does not make sense - UNLESS - not only the company being criticized, but algaefix, pool algaecide manufacturers, fish farmers, etc - according to research - they are totally involved in some sort of conspiracy. Every mention of the product (lets pretend Busan 77) - mentioned - recommends repeated dosing. If so - are all of us with pools putting our kids at risk? etc etc etc - name your application. IMHO - the testing you are doing now - in comparison to suggesting that Vibrant is similar to algaefix - has not been scientifically verified as to method, replicated, etc . Are you also suggesting NOW - just curious - that algaefix should not be used in a tank - because it accumulates? Based on the results. Forget Vibrant - You've decided that Vibrant and Algaefix are 'the same'. They also recommend multiple doses - as does my pool algaecide.