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Hold My Beer While I Detoxify This


HH Morant
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Dechlorinators dechlorinate water almost instantly. They are great products. Do they detoxify ammonia? I am convinced they do not.

Let me explain why I don’t believe.

First, there is nothing wrong with being a nonbeliever. Do I feed my fish two or three times per day because that's what the fish food label says? No. Do I replace my biological filter media every two months because that is what the manufacturer says I must do? No, of course not. Bacteria in a bottle says it will instantly cycle your tank. Yeah, right.

It is part of my job as a fish keeper to evaluate manufacturer claims and reject those that don't make any sense.

Manufacturers put things on the label to make you use more of their product. Sometimes their claims are not accurate. We all know that.

There are at least two manufacturers who claim their products “detoxify” ammonia - Seachem and Fritz Aquatics. Natural Rapport water conditioner claims it removes ammonia and nitrites. API Ammo Lock is another such product. There are more. They all have secret proprietary formulas, and they all claim to detoxify ammonia.

The claims involve chemistry and chemical reactions, so they are difficult for most people (me included) to evaluate. We have to read what chemists say about these things. Anecdotal accounts - "I used it and my fish did not die"- are not science.

The author of aquariumscience.org convinced me that the claims of these manufacturers are false. He did tests on 11 different water conditioning products. He describes the tests in detail. He used Seachem's tester to determine whether any of the products detoxified ammonia. They did not.

Please read the articles. I think they are convincing.

The author of aquariumscience.org is a chemist who has lots of aquariums and has kept fish for decades. He has written over 300 articles addressing many subjects of interest to aquarists. He has made them available to everyone for free. He does not sell advertising and he does not make money from his website. He explains that chemically there is no way the ingredients in water conditioning products can detoxify ammonia or nitrite. His tests confirm that they don’t.

But the guy at aquariumscience.org is not the only one who has tested claims that dechlorinators or other water treatments detoxify ammonia/nitrite.

A post by Taricha on the Reef2Reef blog (reproduced on aquariumscience.org in the article titled “Prime, Safe and Ammonia”) describes in detail a series of tests by two posters  (Taricha and Dan_P) which come to the same conclusion – Prime does not detoxify ammonia.

Another chemist posted on the Aquarium Co-op forum making the same point: it is not chemically possible that any water conditioner detoxifies ammonia. In a thread entitled “How does Prime work,”@DShelton explained in a 5/11/21 post that there is no aquarium-safe chemistry to make ammonia safe.

Do I believe these four people? Yes I do. I do not believe they are comic book villains who are scheming to murder our fish. Do I believe that Prime does something that – in the manufacturer's words – is "unexpected chemically?" Well, no, I don’t.

Here is @DShelton’s 5/11/21 post in full:

Let me preface this in two ways:

  • I have no axe to grind with Seachem, they make some fine products, many of which I buy and use. I do have an issue with their marketing on some products, especially prime.
  • I am a degreed chemist.

I think everyone can agree that most municipal water supplies in the US will contain either 'chlorine' or chloramine, and those two chemical species are bad for fish and inverts.

When gaseous Cl2 is added to water, it reacts with the water like shown in the following two equilibria:

Cl2 + H2O  <--->   HCIO + H+ +  Cl−

HClO  + H20 <----> H3O+   +   ClO-

Reduction is the chemical process by which the dechlorinators work. They 'reduce' the chlorine species (CLO-) that are in water (as an anti-bacterial agent) to the harmless Cl-, and as the ClO- is consumed, both of the above equilibria are driven to the right.

 The two most common active ingredients in most commercial dechlorinators is either sodium dithionite, or sodium thiosuphate. The chemistry is below:

thiosulphate is one of the products of the decomposition of dithionite in water, so whether your dechlorinator starts with dithionite or thiosulphate, the chemistry is the same.

sodium dithionite          thiosulphate

2 Na2S2O4 + H2O ---> Na2S2O3 + 2 H2SO3

The thiosulphate reacts with hypochlorite in water:

Na2S2O3 + 4 NaClO + H2O ---> H2SO4 + Na2SO4 + 4 NaCl

2 H2SO3 + 4 NaClO + H2O ---> 3 H2SO4 + 4 NaCl

I think you will recognize that final component of both of those equations as common salt, but the key thing here is it has been 'reduced', i.e. its oxidation state has changed from being positive (in the hypochlorite ion) to being negative in the chloride ion. This is what I mean when i say they contain reducing agents. They cause a chemical reduction (gaining electrons).

 Now the second half of the chemistry, and the part which is marketing garbage, relates to its ability to 'detoxify' ammonia. In an aqueous solution (i.e. water) gaseous ammonia exists in the following equilibrium:

 NH3   +   H2O    <------>    NH4+  +  OH

 That particular equilibrium is pH and temperature dependent, but the key thing here:

  • gaseous ammonia is toxic at ~.5 ppm total concentration.
  • NH4+ is also toxic, but at much much much higher concentrations (dependant on pH)
  • all of the titration based test kits (API, sera, etc) measure that concentration as a total, i.e. NH3 and NH4 together, so the test kits are not giving you the big picture. (The Seachem ammonia alert measures free ammonia. It is the one that hangs in the tank and is a good product since it is free ammonia)

 What is actually happening in almost all aquaria is:

 In just about all aquaria with a pH <  ~8.5 or so (which is a huge number of them;  here in N. Texas my tap ranges from 8.0 to 8.2) most of the ammonia (NH3) will exist as ammonium (NH4+). Free ammonia gas, actual NH3, is toxic at ~.5ppm.

A variety of factors (pH and temperature) will affect how much of the NH4 is free NH3 in solution, but in aquarium conditions, it is safe to approximate between .1 and 1% of total as NH3. In other words, your .25ppm "ammonia" as shown by the test kit, at your pH is less than 1% of that as free ammonia.

 So in other words, the prime is not 'detoxifying' the ammonia. There is just not enough ammonia in the water for it to be toxic. Using the example that @Solidus1833gave of 2ppm total ammonia in their tap water. The actual amount of free ammonia was between: .02 and .2ppm which is not toxic. The prime did nothing.

 The only way to truly make the ammonia safe is for it to be oxidized from NH3 ---> NO2-   ---->  NO3- and to my knowledge there is no aquarium safe chemistry to do this, beyond the Nitrosomas and Nitrobacter doing so through the nitrogen cycle.

 EDIT: I am sure there are some typos, I was typing furiously to get it posted.

Edited May 11, 2021 by DShelton

 

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I took several sips from your beer whilst holding.

Excellent chemistry rant! I am not qualified to prove you right, but I think you’re probably right. I’ve always wondered what companies would have to add on their labels for beginning aquarists to cry foul?

”Detoxifies chlorine, ammonia, and halitosis!”

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I’m not a chemist and can’t comment if it’s right wrong or not. I never trust any product. To me ammonia or nitrite means water change or a series of. I never quite “got” the detox stuff we didn’t use conditioner back when dinosaurs roamed the earth and I first started. I would not hand a drowning person an inhaler and hope they make it until I get around to doing CPR. Thanks for the post and chemistry lesson. I often wondered how it’s claims for so many miracles could be true. I actually posted the question a few months ago about the differences in products and if they did more than fix chlorine issues. 

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On 2/22/2022 at 12:32 PM, HH Morant said:

The claims involve chemistry and chemical reactions, so they are difficult for most people (me included) to evaluate. We have to read what chemists say about these things. Anecdotal accounts - "I used it and my fish did not die"- are not science.

Its difficult to evaluate because the ingredients are "trade secret". 

 

On 2/22/2022 at 12:32 PM, HH Morant said:

The author of aquariumscience.org convinced me that the claims of these manufacturers are false. He did tests on 11 different water conditioning products. He describes the tests in detail. He used Seachem's tester to determine whether any of the products detoxified ammonia. They did not.

His/her "tests" just show that they do not decrease the measured amount of ammonia on those assays.  They don't prove one way or another that they detoxify ammonia.  You'd need animals to do that study. 

That author also claims that he knows prime et al are "100% a chemical called sodium dithionite (Na2S2O4)."  He claims to have proof but won't share the data and claims he's right because he used an expensive spectrometer (which can show two things are different, but can't prove two things are the same).

It's also suspicious when someone says something is a "fact of science". 

There are also other ways "detoxification" happens.  Look up how adding salt "detoxifies" nitrite.  or how febreeze works (its actually not just a smell to cover up other smells).

 

On 2/22/2022 at 12:32 PM, HH Morant said:

The author of aquariumscience.org is a chemist...

He or she claims to be a "degreed professional chemist".  Thank can mean a lot of things and you can have a lot or a little knowledge of chemistry and still describe yourself that way.  I've shared my opinion about the author of aquarium science before but in short I don't trust him any more than seachem. 

 

 

 

In the end, I'm not convinced one way or the other on this.   Until someone does a study with live animals, or provides the ingredients and plausible chemistry, I'm not going to be satisfied I know one way or the other.

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I have always secretly questioned Prime's claims of detoxification as well. I think @CT_makes a good point that I was thinking about as well when I was reading the OP. There is a difference between getting rid of the ammonia and detoxifying the ammonia. I still think your argument was well laid out and made a lot of sense though. I can't speak for the specific studies as I have not read them, but if what they were testing is getting rid of ammonia then that is different than Prime's claim. I would say this definitely intensifies my suspicions of its claims though. It has always seemed a bit odd to me but I didn't have the science to back it up. My conclusion, so far, is it is still POSSIBLE that it DETOXIFIES but I remain skeptical and possibly even more so after reading this. I would be interested on what you think about the detoxifying vs getting rid of ammonia though as you clearly have a better scientific background than mine. 

Edited by Cinnebuns
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I think @CT_ is right to be cautious of blindly accepting the findingson AquariumScience. The internet is full of nonsense. The thing that sways me most is that the author isn't trying to sell anything. Nor are they really trying to push people away from Seachem products. If they were pushing their own dechlorinator, or another company's, I'd be extremely skeptical of their findings. 

The gist of their research seems to be that Prime works well for its intended purpose but doesn't live up to the marketing speak. If I recall correctly, the most product pushing they do is toward another Seachem product: Safe. Mostly because it's shelf stable and goes further per bottle.

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Like @Schwack and @CT_, in an era when misinformation is rampant and someone waves their credentials in the air and expects us to take it on faith alone, I'm really wary of aquariumscience.org. I personally feel a lot of his information is misleading at best. He does not create rigorous study designs and IMO his own 'research' is akin to anecdotal accounts without peer reviews and replicable lab work to back it up. As a former statistician I cringe a little when I look at his articles. That isn't to say that some of his stuff doesn't have truth to it, I just wouldn't rely on him as a primary source.

I've also heard through the grapevine and screencaps of his conversations on reddit that the guy is rather unsavory to speak with one on one and tends to fall back on petty insults with people who disagree with him or ask for further documentation. Not a fan.

Regarding Seachem Prime and its claims, I don't really see any reason to doubt it, but I'm inclined to rely on water changes in the presence of ammonia/nitrite and not Prime alone.

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On 2/22/2022 at 6:06 PM, laritheloud said:

I've also heard through the grapevine and screencaps of his conversations on reddit that the guy is rather unsavory to speak with one on one and tends to fall back on petty insults with people who disagree with him or ask for further documentation.

I can tell from some of his own posts that this would be very possible.  I hate how pompous he comes across when he talks about his credentials, but I find most of his posts to be at least a good starting place.  I don’t ever take anything off the internet as gospel since there is so much misinformation out there.

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Thanks for taking the time to write that, I use prime because it's the best value dechlorinator I can get easily I was always dubious about the temp binding claims as surely if it could really do that it would have a secondary dosage instructions. 

So thanks for providing some facts for my natural suspicions. 

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On 2/22/2022 at 7:14 PM, Odd Duck said:

I can tell from some of his own posts that this would be very possible.  I hate how pompous he comes across when he talks about his credentials, but I find most of his posts to be at least a good starting place.  I don’t ever take anything off the internet as gospel since there is so much misinformation out there.

Agree. He has provocative angles and there are some good points in his site, but it's best to take a critical and skeptical approach to his articles the same as any other rando on the internet. 😉

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On 2/22/2022 at 6:35 PM, laritheloud said:

Agree. He has provocative angles and there are some good points in his site, but it's best to take a critical and skeptical approach to his articles the same as any other rando on the internet. 😉

Exactly.  Until he is ready to publish studies properly and submit them fir peer review, publish his full credentials, etc, then it has to be taken with some skepticism.  And yet, still a decent resource despite all the shortcomings.

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On 2/22/2022 at 4:18 PM, Cinnebuns said:

I would be interested on what you think about the detoxifying vs getting rid of ammonia though as you clearly have a better scientific background than mine. 

Hold my beer while I explain.

I am not a chemist.

Free ammonia is a chemical compound which is toxic to fish. If it is free ammonia, it is toxic. To make ammonia non-toxic, you must change the chemical compound into a different chemical compound - one which is not free ammonia. 

When the three writers described above used the Seachem test to measure free ammonia and the test showed free ammonia was present, they knew that it was still toxic, despite the addition of Prime or the other products tested.

When you pour something into your aquarium, you are not removing anything. You are adding something - in this case, something that you hope will change free ammonia into something else - some chemical compound that won't hurt your fish. This change would have to be brought about by a chemical reaction which should be predictable by chemists, who are the experts in this field.

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@CT_ is absolutely right.

As OP said, dechlorinators  release chloride when they come in contact with chlorine. Chloride doesn't affect ammonia or nitrite directly. Instead chloride binds to receptors in the fish and prevents nitrite and, to a lesser degree, ammonia uptake which effectively detoxifies them relative to the fish's biology.

Or more accurately, chloride (in very very small amounts) dramatically increases the tolerable concentration of ammonia and nitrite for the fish. The detail here is that is only works when chlorine is present meaning it won't do anything in aged water.

All the "tests" and chemical equations from chemists miss the mark by quite a lot. To disprove the claims of Prime, you need to do LC50 tests with controls on live animals. But if the chemical equations that are usually cited by these chemists are true, then tests don't need to be done because the affects of chloride on ammonia and nitrite toxicity are proven.

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As for Aquariumscience.org

It's very odd to me when people say he has no 'real' testing or whatever, and say he should not be trusted for whatever reason. These same people completely ignore the MANY scientific articles he quotes! This guy does not just make stuff up, he studies it then writes what he finds. I can personally tell you I have read a few scientific test and studies that he has written about, he's not making it up. Just the other day I was reading up on Discus fish's behavior in the wild, a long study by some biologists. I'm positive this is where he got his information. Again, it's not made up. Then there are times in his writings he says flat out, "this is my opinion, it's not scientific fact".   

If you believe whatever Seachem says I've got a bridge in Brooklyn I'll sell you cheap. 

Also, like what some others have said, he has ZERO to gain, there isn't even one small advertisement on his site. On the contrary, what do companies like $eachem stand to gain? Hmmm, let me think ,,,,, could it be $$$$$$$?!

Also, there is a LOT of logic in his writing too that I can tell you that you sure as heck will not find on an aquarium forum. People repeat some pretty silly stuff.

Aquarium supply companies can tell you anything they want, they are not regulated except by the all mighty dollar and their shareholders. 

Someone said, I have heard he 'talks to down to people' or what ever. What on earth does this have do with him being right or not? 

Just FYI, I've read his replies at the end of the front page on his site and people correct him all the time! He tells them thank you every time too and reflects the changes to his site.

I can tell you I'm no chemist but I'm glad I have a place to turn that has an author that is one and can study scientific papers (that are over my head) and put in down in a way I can easily understand. I am VERY happy I found his site!

Happy Fish Keeping!

 

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On 2/22/2022 at 5:17 PM, modified lung said:

@CT_ is absolutely right.

As OP said, dechlorinators  release chloride when they come in contact with chlorine. Chloride doesn't affect ammonia or nitrite directly. Instead chloride binds to receptors in the fish and prevents nitrite and, to a lesser degree, ammonia uptake which effectively detoxifies them relative to the fish's biology.

Or more accurately, chloride (in very very small amounts) dramatically increases the tolerable concentration of ammonia and nitrite for the fish. The detail here is that is only works when chlorine is present meaning it won't do anything in aged water.

All the "tests" and chemical equations from chemists miss the mark by quite a lot. To disprove the claims of Prime, you need to do LC50 tests with controls on live animals. But if the chemical equations that are usually cited by these chemists are true, then tests don't need to be done because the affects of chloride on ammonia and nitrite toxicity are proven.

I gotta say, this is really reaching. Heck, just put salt in the water then.

Funny coincidence, the author of aquariumscience.org writes about salt decreasing the toxicity of nitrite. I read it a few months ago. 

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On 2/22/2022 at 3:52 PM, Schwack said:

Nor are they really trying to push people away from Seachem products.

If I remember what I read of that website they overtly state they're not against seachem but there's STRONG subtext against seachem as an entity.  But that's subjective, especially in writing.

 

On 2/22/2022 at 5:03 PM, HH Morant said:

To make ammonia non-toxic, you must change the chemical compound into a different chemical compound - one which is not free ammonia. 

I think that depends on what you call a chemical compound.  I think the (intended or not) reading of that sentence sounds like you're saying you can't "detoxify ammonia" without converting it to something else.   Ammonia hydrogen bound to something else is still ammonia and may still assay as ammonia if its energetically favorable but could be non toxic.  But without a proposed mechanism I'm really just speculating. 

 

On 2/22/2022 at 4:41 PM, Odd Duck said:

Exactly.  Until he is ready to publish studies properly and submit them fir peer review, publish his full credentials, etc, then it has to be taken with some skepticism.  And yet, still a decent resource despite all the shortcomings.

I'd give him/her more space than that.  Individuals can publish in journals but the academic system doesn't support that or make it easy.  And on the flip side anyone can dump something into a predatory journal.  I'd be happy with good, well described methodology, citations for all the "scientific facts", actual data rather than conclusions, and maybe some figures (other than random fish photos every 3 paragraphs) and photos of setups for clarity.  Science relies on idea that the person writing it is honest so IMO that gets the benefit of the doubt unless things can't be reproduced, and even then I'd err on honest mistake first.

On 2/22/2022 at 5:55 PM, HH Morant said:

Prime claims that it does work in aged water. I have never seen any claim by Prime or any other manufacturer that the product works on the fish and not the ammonia.

I think "works on the fish" is just an intuitive way of thinking about on possible mechanism and not a literal thing.  "detoxify" is a vague word that speaks to the toxicity, which itself is kinda vague, so there's a lot of rhetorical wiggle room.

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On 2/22/2022 at 6:28 PM, Wrencher_Scott said:

If you believe whatever Seachem says I've got a bridge in Brooklyn I'll sell you cheap. 

I'm dubious of a lot of their claims. 

On 2/22/2022 at 6:28 PM, Wrencher_Scott said:

Aquarium supply companies can tell you anything they want, they are not regulated except by the all mighty dollar and their shareholders. 

and the FTC, and local and state laws.  AFAIK the AG in every state will prosecute companies that are behaving badly.  These claims if wrong would be false advertising (I think, IANAL), but someone would have to prosecute, either the FTC or the GA attorney general's office, or I think a citizen that's been harmed by the claim.  I'd love to see that happen.  We may learn through a lawsuit how prime and others work or don't work.

 

On 2/22/2022 at 6:28 PM, Wrencher_Scott said:

Someone said, I have heard he 'talks to down to people' or what ever. What on earth does this have do with him being right or not? 

Tone and style can speak to motivation or potential bias or affinity for conspiratorial thinking.  Its a very soft indicator but I feel it does weaken his/her credibility, deserved or not.

On 2/22/2022 at 6:28 PM, Wrencher_Scott said:

Also, like what some others have said, he has ZERO to gain, there isn't even one small advertisement on his site. On the contrary, what do companies like $eachem stand to gain? Hmmm, let me think ,,,,, could it be $$$$$$$?!

Money isn't everything.  He could genuinely be trying to help the community.  But by the same logic as above that doesn't make him right.

 

On 2/22/2022 at 6:34 PM, Wrencher_Scott said:

Funny coincidence, the author of aquariumscience.org writes about salt decreasing the toxicity of nitrite. I read it a few months ago. 

This is true as far as I can tell, but its not because it changes the nitrite.  Something similar may be true for ammonia and trade secret chemical X.

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On 2/22/2022 at 6:58 PM, CT_ said:

I'm dubious of a lot of their claims. 

and the FTC, and local and state laws.  AFAIK the AG in every state will prosecute companies that are behaving badly.  These claims if wrong would be false advertising (I think, IANAL), but someone would have to prosecute, either the FTC or the GA attorney general's office, or I think a citizen that's been harmed by the claim.  I'd love to see that happen.  We may learn through a lawsuit how prime and others work or don't work.

 

Tone and style can speak to motivation or potential bias or affinity for conspiratorial thinking.  Its a very soft indicator but I feel it does weaken his/her credibility, deserved or not.

Money isn't everything.  He could genuinely be trying to help the community.  But by the same logic as above that doesn't make him right.

 

This is true as far as I can tell, but its not because it changes the nitrite.  Something similar may be true for ammonia and trade secret chemical X.

False advertising? Oh please. Does that ever happen and do you think that is any kind of deterrent? Really? Have you ever seen ads on late night television? That ain't gonna happen.

Conspiratorial thinking? Tone and style? Are we going to psychoanalyze the guy now? lol  Besides, he thanks people that correct him.

Here you go, from his site. Read it you might learn something. I know I did. 

https://aquariumscience.org/index.php/5-3-safe-nitrite-levels/

One solution for nitrite spikes is to add a small amount of salt. The chloride ion competes with the nitrite ion for absorption into the gills so the fish are protected against the nitrite. For the dosage measure the nitrite level in parts per million (ppm). Divide the ppm by eight. This is the number of level teaspoons to put into each ten gallons of aquarium water to detoxify the nitrite.

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On 2/22/2022 at 6:34 PM, Wrencher_Scott said:

I gotta say, this is really reaching. Heck, just put salt in the water then.

Funny coincidence, the author of aquariumscience.org writes about salt decreasing the toxicity of nitrite. I read it a few months ago. 

You're right, just put salt in the water. SeaChem is trying to capitalize on a byproduct of dechlorination. What they don't tell you is a water change is still necessary to get this effect which makes using it pointless in most situations.

I brought it up not to defend Prime but because these chemists that think they are disproving Prime works are actually unknowingly proving it does work at least in certain situations. That's because they are completely ignoring what's by far the most important variable—the fish.

After all, when something is said to be toxic, that means it's toxic to a living organism, like a fish for example. You can't do a toxicology test without involving a living organism. Otherwise you're just doing a chemical test. That kind of methodology in a toxicity test would be laughed out of a science journal in a nanosecond.

Interesting that the aquariumscience.org guy is aware both that dechlorinators release chlorides and that chlorides detoxify nitrites. I smell an agenda.

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On 2/22/2022 at 7:22 PM, Wrencher_Scott said:

False advertising? Oh please. Does that ever happen and do you think that is any kind of deterrent? Really? Have you ever seen ads on late night television? That ain't gonna happen.

You'd be surprised.  It doesn't always make the 5-o-clock news but it does happen and often times companies fix or settle things out of court.  If you look close advertisers will often toe the line between puffery (a legal term, apparently) and lies.  Outright lies are not okay.  That's not saying seachem doesn't lie, just saying it is a deterrent, if only an imperfect one.

 

On 2/22/2022 at 7:22 PM, Wrencher_Scott said:

Conspiratorial thinking? Tone and style? Are we going to psychoanalyze the guy now?

No. but people do this was in context of arguing that he has not motives to lie.  Which is something that I'm not arguing for or against its easy to be wrong without lying.

 

On 2/22/2022 at 7:22 PM, Wrencher_Scott said:

lol  Besides, he thanks people that correct him.

laughing at me I guess appeals to my ego so I can't argue with that point.  He does thank people some times says they're wrong other times.  I don't blame him either way.  It doesn't change the original point though.  And on at least on point that seachem themselves corrected him he said they were wrong.

 

On 2/22/2022 at 7:22 PM, Wrencher_Scott said:

Here you go, from his site. Read it you might learn something. I know I did. 

https://aquariumscience.org/index.php/5-3-safe-nitrite-levels/

I already said I believe this and as far as I can tell its true.  I've read a lot of that site and find it intriguing and full of good ideas.  I just don't take everything it says as canon and find portions of whats written unsupported to my personal satisfaction.

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