Copper Sticks to Glass - Toss Out Old Tanks

[leebca]

So what's the take on the statements by Dr. Shimek and Randy Holmes-Farley regarding copper adsorbing onto glass?

This ReefCentral thread according to Dr. Shimek:
http://reefcentral.com/forums/showthread.php?s=&threadid=192487&highlight=copper+AND+acid

This is a thread from ReefCentral where Randy Holmes-Farley mentions it:
http://reefcentral.com/forums/showt...ight=adsorbed+AND+copper+AND+glass#post459830

The underlying case is that copper will adsorb (lay on the surface -- NOT absorb: going inside the glass) and stay there even after copper has been removed from the tank and the tank washed out with household cleaners.

Once the aquarist thinks the tank is 'clean' they proceed to use the tank for a reef system only to find that their invertebrates are dying off.

The belief is that in the new aquarium system, the adsorbed copper comes out into the water. This copper level is below the measuring ability of test kits, but high enough to either kill the inverts outright, or to slowly kill them from the low-level exposure.

In order to make the tank ready for a reef, it has to be cleaned with very strong acid and other 'un-safe to use' chemicals. Thus either clean the glass like prescribed or don't use it again for an aquarium.

Anyone have any knowledge or experience along these lines?

I wonder if it makes a difference on the kind of copper medication used, or not?

 

[wrightme43]

I dont buy it, but then again, This reef here was up for 1.5 years in a tank that I had chiclids in, and used copper in.

 

[wrightme43]

As you can see everything is dead. LOL

 

[Elmo18]

No copper for me thanks....

I just tossed out a 10 gallon medicated tank because of copper usage...

I use it in QT....and it makes me leary when buying used tanks...because of the things stated above.

Best,
Ilham

 

[jsmkmavity]

if you look at a tank that used copper you might notice the silicone sealant in the corners is blue. my understanding is this is where the copper is absorbed not the glass, but i have no scientific data to back it up.

 

[Curtswearing]

Copper is readily adsorbed to just about anything in your tank. Powerheads, pumps, PVC or rubber plumbing, glass, silicone, sand, LR, etc. That's why you don't want to put it into your display tank...only a QT tank. I think a lot of the problem is that it deadsorbs fairly slowly so people don't realize that it is building up in their tanks. Additionally, it kills inverts slowly. I.e. it's like smoking vs hemlock. One kills you slowly over time and one kills you instantly.

Consistent use of Carbon and Polyfilters will help substantially. If this is to become a reef tank, Seachem's Cuprisorb is the order of the day.
While Steve had good luck with his tank, I've read of many people who've had horrible luck with tanks that were treated with Copper.

 

[leebca]

The value of Poly Filters is questionable in this scenario. We have to appreciate what the limits of this product are and what the manufacturer says they know about the product.

Dr. Shimek says that some invertebrates can't even handle copper as low as 1-5 ppb. If you subscribe/believe that the reports of copper in concentrations of a little as 1-5 ppb can slowly or outright kill invertebrates, then Poly Filters do little good in this scenario.

The makers of Poly Filters, Poly-Bio-Marine, Poly-Bio-Marine, claim that their Poly Filters will NOT remove all copper. Their filters are incapable of removing copper below ~30 ppb. That level would be capable of chronic toxicity for many invertebrates. Dr. Randy Holmes-Farley discusses the Poly Filter issue in this thread on Reef Central:
this thread on Reef Central.

In reviewing the manufacturer's website, you will find a statement that their Poly Filter is designed so as NOT to remove all trace elements.

There are those that say that even though glass is a problem, acrylic and most plastics do not adsorb copper, making those things made of those materials a non-issue in this scenario.

A lot of opinions are flying around, but how much is actually known? I don't know. :evil:

 

[leebca]

jsmkmavity,

I think that concept of silicone sealant retaining copper is fairly well believed. It is the same for methylene blue. Use a medication containing methylene blue and the sealant will turn a (nice) bluish color.

But the issue is the glass itself being a problem to the point that either you have to perform unsafe cleaning operations on it, or you should not use it again for any kind of reef system (which would contain invertebrates).

What perplexes me. . .If it takes that much effort and strong chemicals to get the copper to de-adsorb from the glass, then how much of it could reasonably be coming off on its own, into the seawater that would make it so bad that it would be better to throw away the tank?

 

[Boomer]

Lee

I agree. In 30 some years of having tanks that have had loads of cooper I have yet ever seen or known any inverts to die from copper. I say this based on I have keep many inverts, some of them for up to 15 years. IMHO this copper issue is blown way out of proportion.

 

[leebca]

I've been in contact with friend Bob Goemans. I'd like to post his reply, since he has given his permission to do so.

Hi Lee,
Now keep in mind that I’m not a scientist, however, I’ve only been in this hobby for 60 years! Furthermore, my scientific knowledge of copper and its affect on various parameters/mediums is quite limited. Yet I believe silicon dioxide (glass) is an oxygen source, and since copper is a conductor, copper will/can react with its oxygen molecules and be retained by the glass to some extent. What that extent is, I don’t know, nor do I know which type of copper, chelated or ionic, have the most impact. Yet I would think ionic. Furthermore, this would/could be termed ‘plating’ which is an adsorption method/process. I doubt very much there is an absorption situation here!

What's more, for the adsorbed copper to be released, it’s my belief it would take a very severe reduction in pH to release the copper, e.g., a pH of 2! And that’s why an acid bath is used in laboratories needing to reuse glass enclosures for further testing.

And in looking back ‘decades’ where I’ve or others have use it in glass aquariums, and thoroughly washed out the glass tanks and reused them for invert aquariums, I do not know of one single invert being harmed! And as I’ve often said in these type situations, if the tank is going to be reused for inverts, wash it out thoroughly and keep activated carbon or a Poly-Filter in the tank as a precaution.

Additionally, I have a good friend who owned one of this country’s finest aquarium stores and who faithfully quarantined all his animals. And he used ionic copper in glass tanks, which were thoroughly washed and often reused to house inverts, with ‘never’ a sign of invert stress. In fact, he used a LaMotte DC-1600 colorimeter and never registered the slightest amount of copper in any of those reused glass tanks!

Hope this helps, and if you would like to post it, you have my permission.
Cheers
Bob Goemans

 

[rudeanduncouth]

While my chemistry is limited, couldn't you just figure out if they copper would bond to the glass? If I still had any of my books I would do it myself. Though I could see an underlying problem since that only about 70% of most glass is silicon dioxide. The other ingredients of glass are generally sodium carbonate and potash. The sodium carbonate makes the glass water-soluble so they add calcium oxide to restore the property. So couldn't someone with a good chemistry background figure this out.

 

[leebca]

I don't think there is any question about whether or not the copper ions adsorb to the glass. They do.

But. . .How strong is that attachment? What does it take to get the copper ion to de-adsorb? If that bond is strong, then is it logical for the copper ion to come off into our aquarium water which is only slightly alkaline? If it does come off in aquarium water, is it enough to make a 1 to 5 ppb solution that would harm inverts?

Experience says mostly there is no concern. If you wash out a tank that has been used with copper medication(s), it is sufficiently clean of copper to use that aquarium for inverts without harming them.

 

[rudeanduncouth]

To me this is all still just anecdotal information. I would like to see the chemistry that explains it.

 

[leebca]

Dan,

Did you read the references in the first post?

Regarding 'bonding' or adsorption issue, you can Goggle topics related to this.

 

[rudeanduncouth]

I did. I read both of the link threads, but there are no references. I just did some searching and I did not find anything particular regarding copper and glass. I even searched on acid baths and still did not find anything useful. I am not saying that they are wrong. I would just like the actually proof behind it. Obvisously both, Ron Shimek, and Randy Holmes-Farley are respected to people in this hobby but them saying it isn't enough. There isn't enough researching and testing done in this hobby and IMO a lot of speculation.

 

[Boomer]

Know one has any evidence of any kind on this issue. The only evidence there is that given buy some of us that have been in this hobby for decades. However, in regards to Randy, it is a know fact that copper is attracked to and is "stuck" onto many surfaces and does like carbonates. I have never seen silicon turn blue from cooper/green or what ever. It will turn from various dyies, such as MG turning it geen.

Would you guys like me to have Randy come here and post a reply on his concerns

There isn't enough researching and testing done in this hobby and IMO a lot of speculation.

It costs money and for most in this industry it is self-defeating. All that stuff Randy does, who has done more than all combined on chemical issues, is on his own time and out of his own pocket.

 

[leebca]

I'd very much appreciate Randy's input here.

My fundamental issue still remains:
If it's that hard to get the copper to come off of the glass, then why worry about it?
OR
If it comes off the glass with regular soap and vinegar washing followed by diligent rinsing, then why worry about what's left?
AND
Why all the countless years have we not seen dying inverts in tanks where we used copper medications?
AND
Does it matter what kind of copper medication (sulfate, chelated, protein bound like in Cupramine) was used as to the cause for concern (if there is a real concern.)

It just seems to me so far to be a tempest in a teapot. :evil:

 

[Boomer]

Done deal

 

[R Holmes-Farley]

Here are my thoughts on copper:

1. Copper in a reef aquarium is going to be strongly bound to organic materials. That is known to be true in natural seawater at normal copper levels. Maybe when you initially blast seawater with unbound copper there is substantial free copper for some period of time, until the copper concentration eventually drops, or the free copper has a chance to find organics to bind to.

2. While free copper may or may not bind much to glass (and likely none to silicone, IMO), organic bound copper will bind to both glass and silicone surfaces. Not into it, but onto it. It would be an interesting experiment to put some clear cured silicone into a copper/water solution to see if it turns blue. My expectation is that it will not, but I've not done the experiment.

3. It is my opinion that it is not too difficult to remove copper from all plastic and glass objects in an aquarium, but specifically not those that are calcium carbonate. A little bleach will remove organics and copper along with them. A little acid (like vinegar) will remove inorganic copper and some of its precipitates (like copper carbonate or oxide/hydroxide). I think all such objects can be reused after such cleaning.

4. Calcium carbonate surfaces are a much bigger concern. Just as magnesium gets onto and actually into calcium carbonate surfaces, copper and other similar ions would be expected to do the same thing. It is not trivial to clean live rock and sand. In most cases, I'd recommend tossing it. If that is just not an option, cleaning it in acid so that you actually dissolve some of the surface away is a reasonable thing to try, and some folks in my forum have done that.



"Why all the countless years have we not seen dying inverts in tanks where we used copper medications?"


I discuss copper toxicity here:

Tap Water in Reef Aquaria
http://www.advancedaquarist.com/issues/jan2004/chem.htm

from it:

"Toxic Metals in Tap Water: Copper

One of the biggest concerns for aquarists considering the use of tap water is copper. Copper is more toxic to marine invertebrates than it is to humans, so the EPA allows more in tap water than an aquarist would want in an aquarium. Specifically, the EPA has an action level at 1.3 ppm copper in tap water, and it is only a big problem (to the EPA) if more than 10% of the homes on the water supply exceed that level. For that reason, water supplies typically report the 90% level, meaning that 10% of homes exceed that stated value. Many also report the maximum level in any home tested.

Table 5 shows copper levels for a small selection of homes for all of the cities in this study. The reason that copper must be tested at the home tap is that most of the copper in public water supplies comes from the pipes in the home itself. Further, newer does not necessarily mean better, as fresh copper pipes might be even more inclined to release copper to the water than those that have had decades to build up protective coatings.

How much copper is too much? That is difficult to say, and certainly varies from organism to organism. In a recent test,5 Ron Shimek added copper to natural seawater and looked at the effect on sea urchin larvae. He found that concentrations above 10 ppb decreased the larval survival after 48 h, and that concentrations above 100 ppb killed all of them. Whether that translates into particular copper levels to be concerned about in typical reef aquaria is open to discussion. Nevertheless, it points out that copper is potentially toxic at levels well below the EPA action level of 1.3 ppm. That hypothesis is well supported by the literature on copper toxicity.6 Canadian Water Quality Guidelines for the Protection of Aquatic Life suggest that copper be kept to less than a few ppb in fresh water, but they do not provide a salt water recommendation. "

 

[mungus]

Randy Welcome to Reef Frontiers!!! Great to have you here!!! That is some really great info on copper. Thanks for clearing up a subject that often times comes with misleading info!!

Welcome Again
Brian