Copper absorbs into glass...no...

[Ninong]

The process Ninong described to get rid of copper I think is way to complex. Why not just by a new tank?

As I said in post #34 above:

It is certainly not something that I would be interested in performing myself. It sounds too hazardous and too labor intensive.

It is, however, the recommended method in the literature for removing every last trace of adsorbed copper from glass.

It is heartening to see that Dr. Randy Holmes-Farley is of the opinion that a less hazardous method involving vinegar and bleach and lots of rinses may suffice for most situations.

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.

[goblin072]

I don't know about CU and glass. I just wanted to state that it is possible to get CU out of a acrlic tank without washing it or even taking the fish out.

I was not sure it was possible, many things on the web led me to believe that copper is near impossible to get out.

A local FS used copper sulfate on my 330g display tank. Yes I know it was a huge no no. They did not know what they were doing. It created a huge mess of dead invertabrates and new cyano feeding off the new waste.

We ran carbon and did huge water changes. After 6 months snails and hermits would die in a few days.

I researched some more and found a product by Seachem called cuprasorb.
I put 750ml of it in my sump and waited 4 weeks. Guess what! My tank has snails, shrimp etc!!! Knock on wood but no deaths in 3 weeks.

I am pretty happy!. They told me it would be a fish only tank forever. Cuprasorb really works.

I found that carbon does very little at taking heavy metals out of the tank, its more for organics. I am keeping cuprasorb in my sump for awhile longer just in case.

[cichlidfort]

Interesting. Although your crabs and shrimp may survive, you may eventually encounter troubles with keeping more sensitive invertebrates such as anemones and sps coral. You should have gotten a refund with your lfs for using copper.

[leebca]

You are connecting what you've observed to the action of a product. That is very common in the hobby. But what you have witnessed may not be what Cuprasorb did.

1. After water changes, use of carbon, etc., the copper was diluted by the time Cuprasorb was used.

2. The actual amount of copper in your water is not known/not tested by an analytical lab (before any treatment; after each treatment; and currently). (Our copper test kits don't measure copper low enough).

3. In order to claim that a product (like Cuprasorb) has had such an impact on 'saving the invertebrates by removing copper' requires measurements of copper before and after it use, not just whether the invertebrate life is living or not. As it turns out, Cuprasorb does remove copper into the parts per billion, but not low enough to protect invertebrates. This has been measured.

4. Facts are needed as to exactly what level of copper affects invertebrates. Then those facts have to be put against exactly how much copper is attached to the tank that can become free again. However, I've found 6. to work for me.

5. Sadly, Cuprasorb and carbon cannot remove copper that has become bonded to the glass or acrylic (or carbonates in substrate and/or rocks). This copper becomes free slowly in very low concentrations, or as the pH shifts. Carbon and Cuprasorb can only remove copper that is in the water, and then only to a certain level (see 3. above).

6. After suitable cleaning of tanks used in a copper treatment, most tanks are suitable for invertebrate life, even without using copper absorbents.

Not all anecdotal information is of low value. Some has led people to collect meaningful data to support observations. But on this particular subject of copper attachment, carbon and absorbents, limits, and effects, there is enough information to say that an absorbent alone is not good enough to make a copper-treated tank water safe for invertebrates. So the observation made may be more of a coincidence of circumstances.

You can test your theory easily. Put copper in a hospital tank as if you were treating for Marine Ich (2 weeks). Take a sample and have it analyzed by an analytical laboratory that will give results to 1 ppb. Treat the water with Cuprasorb per their instructions. Take samples along the treatment time and the final time and again have it analyzed by that lab to 1 ppb. Now we'll have good information to support an observation that has some value.

The above can be repeated with activated carbon to verify if the carbon does any better or worse than the Cuprasorb.

The cost of the above? Maybe $500 in lab tests. With it being so 'inexpensive' why wouldn't the manufacturers of Cuprasorb advertise the test results that show conclusively: their product is better than activated carbon, their product will make it safe for copper sensitive invertebrates? I've not seen them publish such information, so far. But it would solve the dispute, I think.

[goblin072]

I would bet money that cuprasorb outperforms carbon. I did measure the copper levels and also tested using snails. The water changes had very little effect on the copper levels. They dumped 8 oz of copper sulfate in the tank. It must have bound to the substrate and reef insert. As fast as we took out the water it would be right back. The levels were moving painfully slow. Tester snails would die fast.

The test for copper uses a color indicator even though the scale is a bit crude you can see a color to the water that is lighter than the lowest scale. If you do it on my fresh RO mix the water from the test is clear. With low concentrations of CU you can see a faint color. I did a before test on my QT tank. Prior to addin CU it was zero or too low for my kit. With a few drops of CU. I could see a faint color although not enough for the lowest part of scale. A few more drops and it was easy to read.

I tested after carbon and retested and retested. It really did not change much from before to after using carbon.
The copper had a big dip when testing after using the cuprasorb. The only test that I cared about was the snail test. The snails lived. If its just a coincidense I'll take it.

What had not changed in months all of a sudden changed on the copper test and the snail test. This is in weeks not months. I would put snails in each week and they died like clockwork.

My water is RO, if the membranes are good there should not be enough copper to matter.

Maybe anecdotal but I would bet money that under repeted scienfific tests that the cuprasorb does accellerate the copper removal vs not using it and vs carbon. I know that some copper can be removed with carbon, like cupramine but I don't think thats the case for sulfate.

Much of science starts from anectdotal evidense. If there is enough of it they do a study and eventually it gets proven.

I looked around the web for anything giving me hope of getting the copper out without a tank tear down. I wanted to give people hope based on my real (but anecdotal) copper problem.

I don't think cuprasorb is snake oil.

I would like to see a real study on it. As you said it would not be that difficult to do.

My copper tester kit may not be the most accurate in the world but it did show a rapid reduction. I can't think of another reason for why it tesed so low so fast when it was baby stepping down for months with water changes.

It may still be leaching out but the level is low enough to be untestable on my kit and low enough for my snails to live.

I'm a happy camper.

[berkdog]

Maybe it gets into the glass b/c glass is a liquid/solid. Is glass liquid or solid?

[Ninong]

Maybe it gets into the glass b/c glass is a liquid/solid. Is glass liquid or solid?

Dr. Randy Holmes-Farley answered your question in excruciating detail in posts number 30 and 31 in this thread.

[Ninong]

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.

Reading what Randy said above, I believe the distinction between copper adsorption by glass and copper adsorption/absorption by calcium carbonate surfaces (live rock, aragonite sand, etc.) is that the bond with glass is a strong physical bond and the bond with calcium carbonate surfaces is a chemical bond. If I'm wrong in that assumption, one of the chemists in this thread will probably correct me. Lee was asking me to provide him with a link to the chemical equation for copper adsorption by glass and I was unable to answer his question, which is why I asked Randy to respond in this thread.

I think that's why Randy says that it's acceptable to clean glass tanks with a series of bleach and then vinegar scrubs and rinses but that live rock and aragonite sand should be discarded, or at least not reused in an aquarium with inverts. Dr. Ron Shimek's much more labor-intensive and hazardous method of decontamination is based on his experience at a marine research laboratory where standards were much stricter.

[Ninong]

Lee or Randy,

Now that this thread has been resurrected from the dead, here's a question I have often wondered about that you might have an opinion on. If a salt mix contains a metals chelator, such as ethylenediaminetetraacetic acid (EDTA), does that have any effect on the use of copper medications?

[leebca]

It doesn't. Most of the chelating ability of the salt has been 'used' by the metal ions in the salts. The salt quality used to make salt mixes is not high. Their contaminants include elevated levels of metal ions and that usually handles much of the chelating ability of the salt. The rest is imperceptible on a macro level, but may have some effect on a micro level depending upon how 'dirty' the salts are and the quantity of the chelating salts.

When I take a gallon of properly prepared salt water and add a chemically known quantity of free copper ions to it, I cannot detect any 'loss' of the ions from chelation.

The bad news is that my information (above) comes from work done in the 1970's. It may not apply to current salts. Back then Instant Ocean was about all we had and that formula has been refined many times over the decades since then.

[Ninong]

Hi Lee,

Thanks.

As you may know, Instant Ocean used to contain EDTA back in the 1970's and early -80's (it's listed in their own literature, which was incorporated in an article Robert Fenner published in the 1980's). If I remember correctly, it was 0.06 ppm EDTA. From what I understand, they stopped using it in Instant Ocean more than 20 years ago.

Reef Crystals used to list EDTA as being included but then they stopped saying EDTA and started saying a "Metal Detoxifier - to neutralize traces of heavy metal often present in domestic water supplies." They have refused to identify the "metal detoxifier" in Reef Crystals, saying that's proprietary information. I suspect it's still EDTA.

Anyway, I was just wondering if there would be any difference between a salt (e.g. Instant Ocean) that does not contain a chelating agent and one that does (e.g. Reef Crystals). Apparently not, according to what you are saying.

The reason I was wondering about this is because you can't use a salt mix containing a chelating agent if you're running sensitive wetlands studies (e.g, the EPA labs) looking for metals contamination. The last time I checked, the Environmental Protection Agency's purchasing guidelines specified either Crystal Sea Bioassay or Instant Ocean. Neither of those salt mixes contains a metals chelator. I believe the EPA lab in Baton Rouge uses Crystal Sea Bioassay Formula Marinemix.

[Ninong]

Hi Lee,

Thanks.

As you may know, Instant Ocean used to contain EDTA back in the 1970's and early -80's (it's listed in their own literature, which was incorporated in an article Robert Fenner published in the 1980's). If I remember correctly, it was 0.06 ppm EDTA. From what I understand, they stopped using it in Instant Ocean more than 20 years ago.

This is interesting. I just visited Instant Ocean's website again and found a claim that is untrue. I was about to call it Aquarium Systems' website but I guess we should call it Spectrum Brands' website now.

Anyway, here is the claim that is not true:

Q: Does Instant Ocean® contain a dechlorinator? Does Instant Ocean® contain any ethylenediamine tetraacetic acid (EDTA) or other types of metal chelators?

A: Instant Ocean® has never contained a dechlorinator or any type of chelator. It is advisable to dechlorinate using a commercially available de-chlorinator when using tap water to dissolve Instant Ocean®.

Instant Ocean did contain EDTA, a metals chelator. They stopped including it more than 20 years ago. I believe the sea salt bioassay that included that information was authored by Thomas Frakes, who used to run their operations a long time ago. I am almost certain it was 0.06 ppm EDTA.

You won't find this information anywhere on their website because their Sea Water Manual has been rewritten many times -- the current edition is 2009 -- and their link to SeaScope, Volume 1, 1984 is broken. The 0.06 ppm EDTA used to be shown in a bioassay that was included in one of their earlier Sea Water Manuals and it may have been included in the volume one of SeaScope. I know for certain that Fenner photocopied it into an article he published in the 1980's.

I used to have a copy of Instant Ocean's manual that listed EDTA as a component of Instant Ocean salt mix but I lost it during my last computer change. I could always have my source email it to me again, just for the record.