It's Still in the Water!

[Randy Holmes-Farley]

Gee, will I really? Sage advice coming from some one, who has to the best of his published aquarium record, never run an experiment, or done a test.

So, boy, spend some time and spend some money doing the work.

Let's not let this degrade into name calling. As the Vice President of Chemical Research at a pharmaceutical company, as the inventor of approved drugs that you may take yourself, as the holder of many dozen chemical patents, and as a very intelligent scientist, I am quite aware of what it takes to do quality science as opposed to junk science. Have you not read any of my published papers and the experimets therein? Ahh, such a pity.

Since neither you nor anyone else knows what organics are in your tank water, to attribute any found toxicities to metals is simply ignoring the other possibilities. Nearly all organics are toxic at some concentration. Some at very low levels, and some at high levels. Since you don't know what you've got, or what the concentrations are, how can you possibly say that this isn't a real possibility?

To show that it works in a lab is nice. Now does it work anywhere else.

Isn't that what an experiment is? Isn't that what you plan to do? Isn't that even what a reef tank is?

Besides interfering with your current pet theory, why could it not happen in reef tanks if it happens in tanks in labs?

 

[rshimek]

Originally posted by Adam

Adam,

How lucky we are that the collectors target such pollution tolerant variants for the coral trade! How is that more rational than chelation as an explanation?

Pollution tolerant animals abound. We are lucky they do, elstwise our coasts would be barren.

We can keep alive a small subset of all the animals imported, and relatively few species are collected at all. In a lot cases, there are only certain clones (frags) that may be kept alive and well. Hmmm.....

Chelation may work. Prove it. I have given a reasonable explanation of much of the mortality in aquaria, and related it to demonstrable testable source.

If it is not the cause, then let those who suggest that it isn't show that it isn't.

Did you poll the participants in your study to gather some meaningful guage of the health and survival of the animals in their aquariums?

No. I don't think this can be done observation. For example, stress in corals is often measured by increasing respriation rate, and this is impossible for most hobbyists to do.

Such data would be very telling in terms of the real toxicity of these agents in our tanks.

Yes, but it can't be done.

I think the posted abstracts represent far more than mere shreds!

No, they didn't. The have no evidence that such materials are even found in our aquaria, let alone that they are working as suggestted there.

Lastly, I hope that your response to the need for a control was only professional insult over the reminder, and not denial that it is necessary.

Actually it was a comment to the poster, who seems to have remembered that one needs controls in experiments, but seems not to know how to do the experiments necessary to validate his assertion.

someone mentioned testing for heavy metals in skimmate. Elevated concentrations would be pretty compelling evidence for Randys theory.

I have such data and will be publishing it soon... There is not a lot actually going out with skimmates. I suspect most heavy metals are ending up in the tank sediments.

 

[andy-hipkiss]

Guys,

Before descending into the sticks and stones diatribes can we actually take something useful out of Ron's work?

OTS exists IME. Now is it as Bob Stark/Richard Harker suggests related to excessively high bacterial populations or is it in relation to elevated micronutrient levels, or indeed both or none.

As I posted above, measuring Cu or Pb (Zn was also high in my tank but only a paltry :lol: x200 above NSW), I "know" that simple ICP measurements alone do not give the whole story. Chelation certainly would appear applicable as to the reason that I can have x100,000 NSW Cu and still have spawning Acropora. (note to self: I really must submit a Micrpore filtered sample to ICP testing, as we might just be measuring the fact that microalgae contains hugely elevated "trace elements")

However, since as Habib's references allude, some cyano/algae can break the chelation bonds, how "leaky" is this process? Is there an event or trigger that can (in the longer term) lead to excessively high "trace elements" available within the water column?

Perhaps Bob Stark was right all those many years ago on CI$ (fishnet) to suggest replacing 10% (IIRC) of the sand bed per month whether it be in terms of bacteria or "trace elements" ... dunno.

So, for me at least, the question remains, micronutrient levels above NSW are pragmatically not a problem until maybe point X is reached. What is "point X", and how do we avoid reaching that point?

 

[rshimek]

Hi,

Have you not read any of my published papers and the experimets therein? Ahh, such a pity.

And have you done anything that supports what you assert for aquaria?

Nada, I'd guess.

Since neither you nor anyone else knows what organics are in your tank water, to attribute any found toxicities to metals is simply ignoring the other possibilities. Nearly all organics are toxic at some concentration. Some at very low levels, and some at high levels. Since you don't know what you've got, or what the concentrations are, how can you possibly say that this isn't a real possibility?

So why don't you try find out what organics are in tank water. If I don't know them - neither do you and your assertions are valueless.

Oh, I would say it is a possibility. Just an unlikely one. We have known poisons in our systems at known high levels. Pretty good smoking gun, in my opinion.

Isn't that what an experiment is? Isn't that what you plan to do? Isn't that even what a reef tank is?

So... do you have any data that support your suppositions, in reef tanks...

You have no data for types of organic materials in your tanks, and you have no data for their effects on organisms or if they temporarily detoxify metals.

Time to get out of your vaunted Vice Presidente's chair and do some experiments.

I would love to be proven wrong on this, it would be nice to say we can add heavy metals to our tanks and call them additives instead of poisons, and it would be nice to by cheap, bottom of the barrel salt and know it isn't poisoning our systems. Unfortunately, it ain't so.

It is not about a pet theory. The toxic trace metal explanation is reasonable and supported by data, if you - or anyone else - can provide data from aquaria that support your suppositions, let's see them.

 

[rshimek]

Originally posted by andy-hipkiss

Andy,

Chelation certainly would appear applicable as to the reason that I can have x100,000 NSW Cu and still have spawning Acropora.

A more likely explanation is that you simply have a tolerant morph of Acropora.

Chelation might be a factor. Let's see the proof...

That shouldn't be much a problem, if anybody would care to gather the data... I suspect.

However, since as Habib's references allude, some cyano/algae can break the chelation bonds, how "leaky" is this process? Is there an event or trigger that can (in the longer term) lead to excessively high "trace elements" available within the water column?

Of course there is. Chelation of these metals simply provides food for some bacteria, and in the process the metals are back in the water.

So, for me at least, the question remains, micronutrient levels above NSW are pragmatically not a problem until maybe point X is reached. What is "point X", and how do we avoid reaching that point?

According to all physiologists who study corals, and other inverts. "X" is natural sea water levels. Anything above it is dangerous.

 

[sven]

First things first, all the given, given. I do not want or intend to offend or upset anyone with this post.

I believe that all of the contributors are so far over my head on this subject it is like a space-shuttle joke. (So far overhead I don't even know it went by). To illustrate this I would like to suggest to Habib, that even though the first article was "very informative for a large crowd", maybe I should see the "picture book" version. These discussions are extremely informative for most of us that have no means nor the education to perform the research that you all do. Each of you have helped me greatly with answers to my questions in the past and I certainly hope that it will continue. My goal is to be able to help you someday too. No, I won't be able to answer any chemistry questions or identify a mystery invertebrate for you. But someday you may have a question that I can answer. In the meantime. Debate and discussion is a cornerstone of the scientific process. Those who can't listen to or take criticism well are doomed to failure. Obviously you all know what you are talking about. Obviously there is a difference of opinions too. This is all good. I would just like to recommend that you don't get so mad at each other and spend your time sharing the ideas rather than barbs. I believe that there is actually a lot of common ground in what you are saying, just some differences in what it all means. Each piece of research will help to answer that. Just remember, the more personally involved you become, the less you see. And if, heaven forbid, you are proven to be wrong, it is a whole lot easier to show yourself in public in the future.
This is a great topic, those of us on the sidelines can learn a lot. Teach us.

 

[andy-hipkiss]

Ron,

Chelation might be a factor. Let's see the proof...

OK, tell me how I'd go about doing this. Sadly the lab at the place I work is only geared towards elemental analysis of a limited subset of metals (they make high precision wiring and connectors), but if you can tell me how I can take this forward, I'll endeavour to do so.

At the end of the day 211ppm (not ppB!) Cu should mean all my corals are dead ... but they are not. With one eye on the consequences of an event that may make this high Cu level available within the water column, I am keen to contribute.

 

[JohnL]

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[rshimek]

Andy,

OK, tell me how I'd go about doing this.

Frankly Andy, this chemistry is nothing I know how to do.

Now I presume Randy and Habib can do such work, being as how familiar they are with the literature.

I suggest you ask them, or better yet, they do it.

At the end of the day 211ppm (not ppB!) Cu should mean all my corals are dead ... but they are not.

Actually, if my subcontractor who has done chemical analyses for me on environmental projects had come up with such a value, I would suggest that there is an error in the test.

221 ppm Cu will - should - kill everything, chelation or not.

 

[andy-hipkiss]

221 ppm Cu will - should - kill everything, chelation or not.

Indeed. The lab even asked me how come the value was so high. I guess I'll see on Monday when I go back to the office in Belgium and pick up the results of the most recent tests (I had my tank water and a freshly mixed sample of IO tested). I do so hope that they were wrong!

Regarding chelation, Randy/Habib, any suggestions?

 

[wade]

only chelation?

only chelation?

I think a number of valid points have come up, so for my own benefit, and for the benefit of those watching this conversation, I would like to try to outline them again:

- Chelation (biological/chemical? active/passive?) is possibly a major factor in reducing toxicity of various metals.

-Speciation/VALENCE is of specific importance, especially as regards toxicity and ICP tests giving total metals do not consider this.

-Precipitation/complexation is another factor (did that get mentioned in this thread?) that probably plays a real role. Especially as regards copper. CuS isn't toxic until you choke on it (and has a very small ability to return to ionic copper). And yes, in small amounts its likely to float around in our highly kinetic reef tanks.

I believe everyone has made valid points and from thinking about it in the past, I believe that metals are a real concern in 'old tank syndrome'. However, the levels you see in most analyses don't take all avenues of detoxication into account and those must be mentioned. So, before making broad pronouncements and scaring those unable to follow the science, think a little more and dig a little deeper.

Testing for general organics in a reef tank would be beyond even a full length PhD. Its known that many many saponins, terpenes, etc etc are released and look at the volume of slime produced by acroporids.... that alone may play a major role in "resistance" as its shed repeatedly. So why not test the released slime for increased metal concentrations?

I'd suggest the following as far as future posts/articles on the subject... Make certain not to pronounce absolutes. There are too many factors and too many unknowns, especially when someone reaches beyond their immediate education. Bring up the possibility of other mechanisms or avenues. Science is a process of questioning data that others derive, nothing more. Without the questioning its meaningless. When someone asks a question and you have no immediate answer, acknowledge it and allow it as a possibilty unless you can prove otherwise. *steps down from the soapbox*

 

[Randy Holmes-Farley]

So... do you have any data that support your suppositions, in reef tanks...

I have data that there are organic chelators in my tank far in exess of the copper concentration. That's because I add them in the form of large doses of iron citrate.

Beyond that, the problem is analysis. There are literally tens of millions of known organic compounds. Even in well studied natural seawater, there is very little information available on more than the basics of these molecules. People have perhaps studied and quantified a few hundred in seawater.

However, it is generally becoming accepted that metal ions (such as iron) are mostly chelated even in natural seawater. I don't see why that would not be the case in reef tanks, and see real reasons why there would be more chelation based on what we add and what we grow.

Wade:

I think that's a nice summary

 

[Fredfish]

Ahh, its so hard to resist getting involved in a good argu.. er... discussion.

If I understand correctly, nobody disputes that most of these metals provide no usefull biological function. In fact, they are, in the correct form, toxins/polutants/nasty-bad-stuff.

Also, for those that are required to some extent - such as cu - they are found in our tanks in absurdly high concentrations that do not provide any additional value.

If we agree that the above two are correct, does it not make sense to make an attempt to remove or minimize them as much as possible as they provide the potential for problems.

Surely it is reasonable to use a source of salt that minimizes the content of these metals so that we entirely eliminate the potential for problems (or at liest minimize potential risk).


Out of curiosity, how easily do metals change speciation (hope I am using this term correctly)? Is it the same for all metals?

Another question. Will something like the Poly-Filter adsorb chelated forms of these metals (can we really remove them all from our tanks even if we wanted to?)?

Politely and respectfully

Fred.

 

[rshimek]

Originally posted by Randy Holmes-Farley

I have data that there are organic chelators in my tank far in exess of the copper concentration. That's because I add them in the form of large doses of iron citrate.

As an aside, iron seems to be a major algal nutrient and the suggestion that has been made in algology literature, is that the algae don't really use it much, but rather sequester it to prevent bacterial use, as the bacteria that really require iron are primarily cyanobacters which are, in turn, of course, competitors of the algae. So, the question - in I hope a non-confrontational mode - is why add iron? At best, you drive algae, at worst, you drive cyanobacters.

Of course iron hydroxides do detox a lot of the trace metals in at least some natural situations (hot vents) where these are added naturally. So... adding iron might be a good way of counteracting trace element over additions.

However, it is generally becoming accepted that metal ions (such as iron) are mostly chelated even in natural seawater. I don't see why that would not be the case in reef tanks, and see real reasons why there would be more chelation based on what we add and what we grow.

Randy, I agree that at the metal concentrations found in natural situations chelation occurs. That isn't my issue, my issue is that we are dealing with situations where the trace metals are much more highly concentrated.

And additionally, where there is not one shread of evidence that such pathway is occurring in our aquaria, or that if it is, that the chelated byproducts themselves are non-toxic. For you to categorically dismiss the possibility of trace element poisoning without any support for such a position seems, well, absurd.

I think we have a complex soup in our aquaria, where at times both organic and inorganic toxic materials come into play. I have chosen to examine heavy metals simply because I have the seen environment degredation caused by them, and have spent many years in the employ of various consulting firms examing the effects of copper, arsenic, lead, zinc and so forth.

Using methodology that is identical to that found in environmental consulting, I have demonstrated that the heavy metal concentrations in aquaria are sufficiently high to be considered severely polluted.

Bioassays done by other researchers show that metals (again measured the same way) at lower concentrations than in our tanks caused coral death and disruption of coral reproduction, as well as effects in other invertebrates. This means to me, that this could, and probably should be happening in aquaria.

I have provided an explanations for several types of aquarium "maladies" which are consistent with, and supported by the data I have collected. To say that these explanations are wrong is your right, but you have no evidence to support what you are claiming, other than the fact that chelation occurs in natural situations.

In any case, your explanation, still lacks support from aquaria.

 

[rshimek]

Originally posted by Fredfish

Hi Fred,

If I understand correctly, nobody disputes that most of these metals provide no usefull biological function. In fact, they are, in the correct form, toxins/polutants/nasty-bad-stuff.

At any concentrations above those found in natural sea water, they are at best null and at worst poisons. Most of them are considered to be poisons.

Surely it is reasonable to use a source of salt that minimizes the content of these metals so that we entirely eliminate the potential for problems (or at liest minimize potential risk).

Indeed, but no such salts are marketed presently for the aquarium trade. I am trying to change that.

Another question. Will something like the Poly-Filter adsorb chelated forms of these metals (can we really remove them all from our tanks even if we wanted to?)?

I don't know, and will ask.

 

[Sardonic Wit]

Mr. Holmes-Farley:

If there is so much organic chelation going on why should we worry about heavy metals pollution of the ocean and the world's reefs?

It sounds like the metals should be quickly bound up and not pose a threat in any environmental system.

 

[Habib]

copper speciation san diego bay

copper speciation san diego bay

The attached table shows that approx 0.1 % of the copper is present as free or inorganically complexed copper. The remaining copper is bound to organics or is particulate.

 

[cfockler]

If I understand correctly, nobody disputes that most of these metals provide no usefull biological function. In fact, they are, in the correct form, toxins/polutants/nasty-bad-stuff.

Also, for those that are required to some extent - such as cu - they are found in our tanks in absurdly high concentrations that do not provide any additional value.

If we agree that the above two are correct, does it not make sense to make an attempt to remove or minimize them as much as possible as they provide the potential for problems.

Fred, you beat me to it! I was getting ready to post the exact same opinion! :thumbsup:

Nobody has tried to claim that elevated levels of these metals is a benefit to anything. And there is data showing that they are toxins at least in some forms. Chelation and such may or may not be there, but why rely on it to detoxify our polluted water? Why would anybody argue against correcting a potential (and very likely) problem?

I want my tank water to match natural ocean water where feasible. I eagerly await more information on alternative salt mixes and ways of detoxifying my current setup.

And hopefully Ron and Randy will give peas a chance.

 

[rshimek]

Hi,

The point remains regarding chelation in tanks and its relative importance or lack thereof.

Randy has pointed out he cannot test for this. Interestingly enough, then he cannot propose a testable or falsifiable hypothesis. Given that testable hypothesis cannot be formed, he (we, they) have to take this explanation without any sort of verification by the scientific method, which requires testable hypotheses.

So, we have an explanation of events based on documentation in dissimilar systems which must be taken on faith, and on the word of a true believer.

Sounds to me like you guys are creating a religion; The Cult Of
The Totipotent Chelator.

When and if you can use the scientific method to show that this has any effect in tanks I will be glad to hear about it. 'Till then...

Another point as well, if these chelators are being produced by the all of these algae and bacteria, do you not start to wonder why? Simply put it is because the trace metals are damnably toxic to them, too and this is there way of getting rid of them.

Which bears on my point, that if any of these chemicals are in the water in our systems, it is bad news.

 

[rshimek]

Re: copper speciation san diego bay

Re: copper speciation san diego bay

Originally posted by Habib

The attached table shows that approx 0.1 % of the copper is present as free or inorganically complexed copper. The remaining copper is bound to organics or is particulate.

Which simply means it gets eaten by something and kills them during digestion rather than by epidermal absorption.

Six of one, half a dozen of another.