Help needed with Chemiclean and ORP

[Randy Holmes-Farley Verified Community Expert]

The manufacturer claimed mechanism of Chemiclean is by oxidation of Cyanobacteria, rather than the suspected mechanism of an antibiotic.

While it is not proof of the mechanism one way or the other, ORP measurements should at least indicate whether oxidation is plausible.

I’d appreciate seeing data from anyone who has Chemiclean and an ORP probe.

ideally, put the ORP probe in some new salt water and get a reading after it stabilizes (maybe overnight). Then add some Chemiclean and watch for the immediate ORP change.

New salt water is better than tank water because a drop in ORP in water containing substantial bacteria might come from cells breaking open and releasing low ORP contents.

Thanks for any help!

 

[taricha]

I had some chemiclean and ORP probe handy, so I did this before I saw Randy's request so I didn't do what Randy suggested.

I took 500mL tank water, put in autostirrer. After 5 minutes I added 1% (5ml) of skimmate, my reasoning was to give lots of possible targets for an oxidizer to hit to show it was doing something.
Then after it stabilized I added chemiclean vs other oxidizers.

The light blue line was 1 drop of 1/10 diluted Clorox bleach. It Raises ORP in a spike and then lowers as it reacts with compounds in the sample.
Yellow line is 1 drop of 0.01M potassium permanganate showing the same thing - spike rise, and a lowering as it reacts with targets in the water.
Dark Blue is H2O2 which gives the counterintuitive spike-drop that is familiar to those who have measured ORP while dosing peroxide.
Pink is the recommended dose of Chemiclean added around 15 minutes. It did not move ORP in this test at all.

(all samples show a slight lowering when I added the skimmate around 5 minutes)

Again, this is not quite what @Randy Holmes-Farley had in mind, but it makes me think I'd be surprised to find any ORP movement from chemiclean in new saltwater.

Edit: update in post 13 with new saltwater and watching for ORP moves from one day to the next

 

[ScottB]

I had some chemiclean and ORP probe handy, so I did this before I saw Randy's request so I didn't do what Randy suggested.

I took 500mL tank water, put in autostirrer. After 5 minutes I added 1% (5ml) of skimmate, my reasoning was to give lots of possible targets for an oxidizer to hit to show it was doing something.
Then after it stabilized I added chemiclean vs other oxidizers.

The light blue line was 1 drop of 1/10 diluted Clorox bleach. It Raises ORP in a spike and then lowers as it reacts with compounds in the sample.
Yellow line is 1 drop of 0.01M potassium permanganate showing the same thing - spike rise, and a lowering as it reacts with targets in the water.
Dark Blue is H2O2 which gives the counterintuitive spike-drop that is familiar to those who have measured ORP while dosing peroxide.
Pink is the recommended dose of Chemiclean added around 15 minutes. It did not move ORP in this test at all.

(all samples show a slight lowering when I added the skimmate around 5 minutes)

Again, this is not quite what @Randy Holmes-Farley had in mind, but it makes me think I'd be surprised to find any ORP movement from chemiclean in new saltwater.

Ha ha. I was just about to tag you on this.

Might you next start a thread on "How to detect the presence of erythromycin..." ?

 

[Randy Holmes-Farley Verified Community Expert]

Thanks, taricha.

Either there is no oxidizer, or it is a very slow acting one (e.g., O2 is a pretty strong, but fairly slow acting oxidizer) which would seem odd against the observation that it kills cyano pretty fast.

 

[taricha]

Ha ha. I was just about to tag you on this.

Might you next start a thread on "How to detect the presence of erythromycin..." ?

Heh. Appreciate the confidence, but no idea how to detect medications.

However, if erythromycin has enough antibacterial activity, then you ought to be able to detect it by changing how long it takes for bacteria to consume a food and deplete oxygen. What could complicate this is if the antibiotic is not broadly effective enough to noticeably slow down bacterial activity, or if the amount of starches Etc in the excipients that might be present are large enough to feed bacteria more and deplete oxygen faster.

 

[ScottB]

Heh. Appreciate the confidence, but no idea how to detect medications.

However, if erythromycin has enough antibacterial activity, then you ought to be able to detect it by changing how long it takes for bacteria to consume a food and deplete oxygen. What could complicate this is if the antibiotic is not broadly effective enough to noticeably slow down bacterial activity, or if the amount of starches Etc in the excipients that might be present are large enough to feed bacteria more and deplete oxygen faster.

And the gears begin their methodical churn...

Meanwhile, I go about optimizing the cleaning of felt socks.

 

[Dan_P]

Heh. Appreciate the confidence, but no idea how to detect medications.

However, if erythromycin has enough antibacterial activity, then you ought to be able to detect it by changing how long it takes for bacteria to consume a food and deplete oxygen. What could complicate this is if the antibiotic is not broadly effective enough to noticeably slow down bacterial activity, or if the amount of starches Etc in the excipients that might be present are large enough to feed bacteria more and deplete oxygen faster.

Maybe @jda has a slush fund to buy an NMR spectrum of ChemiClean. FTIR might work also.

 

[Dan_P]

Heh. Appreciate the confidence, but no idea how to detect medications.

However, if erythromycin has enough antibacterial activity, then you ought to be able to detect it by changing how long it takes for bacteria to consume a food and deplete oxygen. What could complicate this is if the antibiotic is not broadly effective enough to noticeably slow down bacterial activity, or if the amount of starches Etc in the excipients that might be present are large enough to feed bacteria more and deplete oxygen faster.

Inhibition and acclimation of nitrifiers exposed to erythromycin​

Effects of Antibacterial Agents on Nitrification in an Aquatic Recirculating System​

 

[taricha]

Maybe @jda has a slush fund to buy an NMR spectrum of ChemiClean. FTIR might work also.

Except it was already done years ago. A lab found it to have erythromycin.

The manufacturer didn't claim it then, so no need to give their claims any weight now either, imo.

Haven't seen anything that makes me think it's anything other than what a lab already found it to have. I think people can continue to proceed on the expectation that it's erythromycin.

 

[taricha]

Inhibition and acclimation of nitrifiers exposed to erythromycin​

Effects of Antibacterial Agents on Nitrification in an Aquatic Recirculating System​

Ooh, nice.

 

[Randy Holmes-Farley Verified Community Expert]

I’m not sure how a functional test against bacteria will demonstrate what the active agent is.

 

[jda]

I would not assume that the product is mutually exclusive as erythromycin or an oxidizer.

My memory is not great, but if I recall, somebody found a public PO of a large amount of erythromycin going to Boyd. Boyd denied it, which was the original reefing manufacturer lie. Boyd then printed on the box that the product contained no erythromycin succinate, or at least it did at one time, doubling down on a semi-lie. Of course, there are many other kinds of erythromycin and succinate is usually a suspension and stearate is in powder/pill form (been a long time and I could be wrong on this). Later, somebody had it tested and it did have erytho in it - I have no memory of details or how this was done. Competitors that make similar products also have said that there is erytho in their products. This was all in the ReefCentral days, so that would be where the posts are archived if anybody cares.

Personally, I think that is is erythromycin and some sort of oxidizer. The skimmers go crazy for days or a week after dosing. It does make the water really clear. Even really good GAC cannot strip the water quickly with many reactors on a tank... you just have to wait. I guess that it is possible that erythro is an oxidizer that is not easily caught by GAC and just needs to wait a number of days to break down.

If you wanted to tell me that the erythro killed most waterborne bacteria and the GAC polished them out of the water, then I would believe it.

I have not used it in a long time, but I found it perfectly safe with no side effects other than not being able to skim for a week. It takes a few days for the cyano to fully die. It has not killed it fast when I used it. Usually, the cyano stays the same for the day and just comes back weaker after the lights off/on cycle for a few days.

It has a very unique smell. I don't have any basis for comparison, but I would not be surprised if somebody recognized it. The stuff from BlueVet called like CyanoRx seems to be an exact duplicate for me.

FTIR is not expensive. NMR is expensive and jda is out of reefing money with many kids in college (out of state) and interest rates up (in real estate). Of course, you would have to have something to compare the results against... unless there is somebody who can read the results like people who can read the green falling letters on the screens in The Matrix. With the last go-around with reef manufacturer liar #56, we had another product from an honest manufacturer to directly compare against.

A quick Google search did indicate that there are ways to test fluoroquinolone with color changing things like cobalt thiocyanate, BM blue and ammonium sulfate, but I am not smart enough to make heads or tails out of them or even if erytho worked at all when some others did.

 

[taricha]

...this is not quite what @Randy Holmes-Farley had in mind, but it makes me think I'd be surprised to find any ORP movement from chemiclean in new saltwater.

Update with a few more details.

I did new saltwater as suggested (Instant Ocean). It mixes to a lower ORP (initially 150s) than tank water.
Upon addition of recommended dose of Chemiclean there was no ORP movement, just like with earlier data. Left overnight on slow stirring, the ORP drifted up as it would be expected to with new mixed saltwater, but it was still lower (~220s) than my tank water (high 200s).

adding 10x dose of chemiclean to the day-old new saltwater shows no movement at all either (neither immediate nor over a couple of hours).

The tank water samples with 1% skimmate that had chemiclean added also showed no noticeable movement of ORP overnight. ORP today was still high 200s as it was yesterday.

So, it looks like Chemiclean does not move the ORP of tank water (with lots of oxidizer targets) or new saltwater (many fewer targets) either immediately like common oxidizers, nor over ~a day.

 

[Randy Holmes-Farley Verified Community Expert]

Nice, thanks!

 

[Dan_P]

Update with a few more details.

I did new saltwater as suggested (Instant Ocean). It mixes to a lower ORP (initially 150s) than tank water.
Upon addition of recommended dose of Chemiclean there was no ORP movement, just like with earlier data. Left overnight on slow stirring, the ORP drifted up as it would be expected to with new mixed saltwater, but it was still lower (~220s) than my tank water (high 200s).

adding 10x dose of chemiclean to the day-old new saltwater shows no movement at all either (neither immediate nor over a couple of hours).

The tank water samples with 1% skimmate that had chemiclean added also showed no noticeable movement of ORP overnight. ORP today was still high 200s as it was yesterday.

So, it looks like Chemiclean does not move the ORP of tank water (with lots of oxidizer targets) or new saltwater (many fewer targets) either immediately like common oxidizers, nor over ~a day.

This might be another way to detect oxidizing substances. For your reading pleasure…

Detecting oxidizing agents in urine.

US7445908B2 - Detection of oxidizing agents in urine - Google Patents

A method of detecting oxidants in a biological sample comprising: adding a source of ferrous ions to said sample, whereby the presence of oxidants in said sample oxidize at least a portion of said ferrous ions to ferric ions; adding a chromogenic compound to said sample, whereby said chromogenic...

patents.google.com

 

[taricha]

This might be another way to detect oxidizing substances. For your reading pleasure…

Just for kicks....
"adding a source of ferrous ions to said sample, whereby the presence of oxidants in said sample oxidize at least a portion of said ferrous ions to ferric ions; adding a chromogenic compound to said sample, whereby said chromogenic compound reacts with at least a portion of any ferric ions present in said sample; and detecting for the product of said chromogenic compound-ferric ion reaction"

In principle, rather that the color-changing compound to track the reduced vs oxidized Iron, I could just use my ORP meter - like this... (I think).

This was 500mL of my tank wateron auto-stirrer, at 10 minutes I added a drop of Seachem Flourish Fe (ferrous gluconate) which you can see is in the reduced form of Iron and thus dramatically lowers ORP.
But ORP recovers as the reduced Iron mixes in the saltwater and oxidizes.
at ~15 minutes I added Chemiclean and saw no change to the curve.
At 25.5 minutes, I added H2O2 (at 1mL/40L), and now because the ORP is largely a function of the state of Fe in the sample - H2O2 raises ORP as it is good at oxidizing some of the remaining reduced Iron.

At least that's what I think is going on.

 

[Randy Holmes-Farley Verified Community Expert]

The coffin seems to be getting pretty tightly nailed down.

 

[Dan_P]

Just for kicks....
"adding a source of ferrous ions to said sample, whereby the presence of oxidants in said sample oxidize at least a portion of said ferrous ions to ferric ions; adding a chromogenic compound to said sample, whereby said chromogenic compound reacts with at least a portion of any ferric ions present in said sample; and detecting for the product of said chromogenic compound-ferric ion reaction"

In principle, rather that the color-changing compound to track the reduced vs oxidized Iron, I could just use my ORP meter - like this... (I think).

This was 500mL of my tank wateron auto-stirrer, at 10 minutes I added a drop of Seachem Flourish Fe (ferrous gluconate) which you can see is in the reduced form of Iron and thus dramatically lowers ORP.
But ORP recovers as the reduced Iron mixes in the saltwater and oxidizes.
at ~15 minutes I added Chemiclean and saw no change to the curve.
At 25.5 minutes, I added H2O2 (at 1mL/40L), and now because the ORP is largely a function of the state of Fe in the sample - H2O2 raises ORP as it is good at oxidizing some of the remaining reduced Iron.

At least that's what I think is going on.

I still think you need a couple lab assistants to help you work on all your ideas

Brilliant work as usual.

 

[jda]

If somebody wants to fund the purchases and tests, I can get some of this and some chemiclean and run them up to Colorado State to have some IR run. PM me if there are any benefactors out there who would like to help out. I can do all of the work if somebody can help with the costs.

 

[taricha]

Alternatively, @jda I was looking at the antibiotic residue tests for farm use (milk, eggs, meat etc.)
Some look simple and not too expensive.

ROSA (RAPID ONE STEP ASSAY) FOR ANTIBIOTICS IN HONEY | Semantic Scholar

ROSA is a lateral flow based strip test for the detection of antibiotics that is easily adapted to field/farm testing environments. The test uses minimal equipment (incubator) and can be read visually or with a reader. In the dairy industry, ROSA has gained rapid appeal because testing is...

www.semanticscholar.org

The difficulty seems to be that it looks like the tests for macrolides like erythromycin are not that simple.
They are either way more expensive (Charm Quad2) or there are tests that are simply incubations of bacteria on rich medium where the antibiotic is detected by inhibition of bacteria.
https://nelsonjameson.com/delvotest_p.html

Tests for antibiotics in the hobby would be useful as there are now several cyano removers - or "cyanobacteria stain removers" that say nothing about their ingredients and everyone just presumes (as I do) that they are erythromycin.