Copper - Treatment, Use, Problems

[leebca]

Thanks goodness for copper! Thank goodness that the most troublesome and devastating parasites to our ornamental marine fishes are killed by the use of copper. But it can't be used casually or as a kind of 'answer-to-all' problems. It's use by aquarists comes with the need for responsibility and attention. After all, copper is a poison to our fish and in the effort to kill off the parasites, we can kill off our fishes.

Copper is nowadays used almost exclusively to kill Marine Ich (Cryptocaryon irritans) and Marine Velvet (Amyloodinium ocellatum) infections on our ornamental marine fishes. (I'll use MI and MV to refer to these parasites and the conditions they cause).

I'm sure what is written in this post is familiar to some or all of you, in part or in whole, but it should be clearly stated in one place.


AQUACULTURE DISCOVERS CURE

It's not much of a secret. The ornamental marine fish hobby owes what we know about MI and MV to the studies, research and monies thrown at controlling these parasites, by the aquaculture industry. 70 years ago the aquaculture industry was plagued by these problematic parasites and then it was found that copper could kill both these parasites at a concentration that wouldn't kill many of the food fishes.

One issue that the aquaculturists faced with the copper treatment is how much free copper ions love to complex with carbonates and how lethal it was to the fish. For the aquarist, this means that adding copper in its ionic form to saltwater will cause the copper to attach to substrates, rocks, other carbonate-based things, and even glass! (See Copper absorbs into glass...no...). Treatment with copper requires diligence and control.


COPPER MEDICATION DEVELOPMENT

Copper Salt (Cu2+, cationic or ionic copper)
At first the basic copper medication was a water mixture of a copper salt (e.g., copper sulfate). The copper concentration in this form is hard to control in saltwater. Copper in this form will easily complex with carbonates -- even carbonates that were in the salt water making up the alkalinity! The copper would precipitate out of its dissolved state and no longer be available to do the job of killing off the parasites. These medications I remember well. When added to the aquarium water, there would be a 'cloud' of bluish-white haze in the aquarium water. This was some of the copper coming out of solution.

Controlling the copper concentration in this form was a problem for the aquaculture industry, and a nightmare for the hobbyist. The aquaculture industry had neither the time or the money to keep testing their water to hold the copper in the 'effective range' to kill the MI and MV, yet not kill their stock. This copper was so 'effective' at killing (even fish) that some fish just couldn't even live in the concentration it took to kill the MI and MV. By this, I mean to make clear that the copper in this form is very lethal even to the fish it is supposed to treat. This copper medication isn't even considered a choice by today's standards.

Chelated Copper
The next major development in the medication, was to 'protect' the copper from complexing and coming out of solution so readily with the carbonates in the water. Thus came the 'chelated copper' medications. (Chelated is pronounced KEY'lated). The copper was more reliable for staying in solution. What was done was to shield the copper ion with a weak, very large molecule (e.g., Ethylenediaminetetraacetic Acid or EDTA) The copper ion still complexed with carbonates and the copper still precipitated out of solution, but not as much. The chelated copper was more stable compared to the plain copper salt medications. More fish now could be treated with this form of copper. But the most sensitive of fishes (e.g., dwarf angelfishes, some large angelfishes, some tangs, and scaleless fishes (sharks, rays, etc.)) could not be treated with this form of copper.

Complexed Copper
The serious breakthrough came when the copper, instead of protected by a weak complex in the chelated form, could be chemically bonded to a protein molecule. In this case, the copper is still lethal to the MI and MV, but it keeps an arm's length away from affecting the fish. It resists complexing with carbonates making the concentration much easier to control and to get to remain steady. This copper form could now be used on any ornamental fish, and scaleless fish. This complexed copper is safe and yet effective at killing off MI and MV.



THE NATURE OF THE COPPER

When copper ions get into our aquarium water, they will complex with several other salt water ingredients and some of the things we put in our aquariums. Copper ions, as noted above, are very fond of forming complexes with carbonates. When they do, this complex is not very soluble at the pH of our aquariums and it will precipitate, or come out of solution.

Copper ions will do the same with rocks and substrates that contain any form of carbonate materials. This is one reason why it is best to use copper medications in a hospital tank without such materials.

The precipitated copper-carbonate will redissolve if the pH of our water goes down. This has the effect of suddenly increasing the amount of copper in our tank water. So, the aquarist thinks they are in control of the copper concentration only to find that there is a surge of copper. In addition to maintaining the effective copper concentration, attention has to be given to the holding the pH of the water steady. By the way, this surge in copper, no matter how short of time it is, is enough to permanently injure, poison, or kill the fish being treated.

Another thing has to be made clear about copper as a medication. It is a poison as has been stated previously. Copper can and does cause stress in the fish and thus, does some harm to all fishes at detectable (by test kits) concentrations. [See: Stress (and the Single Marine Fish)]

Copper medications can harm the fish without the aquarist even realizing. In 'effective concentrations' that kill the disease organism, copper stresses the fish and in effect is slowly killing it. Furthermore, (even in low concentrations) copper can stress the fish and weaken it, allowing all sorts of other conditions to affect the fish. I have to be the 'adult' here! Copper is not a toy!

If you decide to use a copper treatment the fish might stop eating. Copper is a stress to the fish and some fish respond by not eating, acting in a peculiar manner, or becoming afraid of its own shadow.


EFFECTIVE CONCENTRATION and TREATMENT

Not only does each type of medication have its own effective concentration, but so does each manufacturer's product. We can't make any general statement about how long to treat or how much copper needs to be in solution for it to do its job. Simply put, only the medication manufacturer knows what they put in the product and thus how to properly use the product.

In short, follow the manufacturer's treatment recommendations very closely.

But no matter what the copper medication manufacturer recommends you need to know what copper concentration range should be used in the treatment. Only the manufacturer knows this.

And since only the manufacturer knows how to properly test for the copper in their medication formula, the aquarist needs to know what copper test kit to use in measuring the copper concentration.

Armed with:
the medication;
having the right test kit for copper recommended by the copper medication manufacturer;
knowing the copper concentration range the manufacturer recommends; and
a bare hospital/quarantine tank
the aquarist is ready to perform a copper treatment. Some manufacturers try to make it easy by just stating in their instructions to add a quantity of their medication per gallon (or per some other volume) to your water, but in the marine aquarium world, everyone's tank is different. One addition doesn't work the same in all hospital tank systems. You need the control of measuring, knowing the target copper concentration range, and holding the copper in that range.


OVER- and UNDER-DOSING

The copper concentration has to be kept in exactly the correct range for it to work properly. As stated above, only the medication manufacturer knows what range is right for their medication. So I can't and no one can say a general/proper range.

In the case of using Cupramine, the manufacturer, Seachem recommends that at first the amount added is half the final dose. Then later the rest is added to bring the concentration to 0.5ppm. FOLLOW THESE DIRECTIONS. Adding half dose allows the fish to acclimate to the addition of copper. After the second dose totally mixes in, then start the testing for copper.

However, if the copper concentration drops below the concentration needed to kill the MI and/or MV, the treatment will have no effect.

Likewise, if the copper concentration exceeds (goes above) the high-end concentration, the fish could suffer, become poisoned, and/or die. This is a situation where clearly, more is NOT better.

For the above reasons, it is important that the aquarist knows how much of the copper is in the water and doing its job. AND must keep it in that range. Any slip means the treatment time has been wasted (and possibly will kill the fish if overdosed).


PERSONAL PREFERENCES

I have my own preferences of these medications. I have used several copper medications since I began keeping saltwater fishes in 1968. With the current advances and availability of good copper test kits like we've never had before, I strongly recommend the use of Cupramine as a copper medication. It is in that third category of being a complexed copper and very safe for use on all ornamental fishes including sharks and rays.

The proper copper test kits to use for Cupramine medication is either the Salifert Copper Test Kit or the Seachem Copper Test Kit. I hear many complaints about how hard it is to read the Seachem Test kit. And the rumors are true that in late 2005 and early 2006 there were Seachem Copper Test Kits on the market that expired before their time and gave erroneous readings. But. . .who's perfect?

The Salifert Copper Test Kit is quicker and easier to use. However, it goes from 0.5 ppm copper indicator straight to 1.0 ppm copper (with no in between comparison color/shading), then the next color is greater than 2. ppm. Cupramine is best used between 0.3 and 0.8 ppm. So this scale doesn't give you much information. You can use Cupramine very effectively at 0.5, though 0.6 ppm is preferred for the 'tougher fishes.' For sharks, angelfishes, etc. 0.3 to 0.5 ppm would be preferred, in my opinion. There is a way around this test kit situation.

If you prepare freshly made up saltwater (like you were doing a water change) and test that for copper, you can then use that to dilute your tank sample water for the Salifert Copper test, remembering to account for any copper reading of the freshly prepared water. Thus, you can get the relative accuracy you need from the Salifert Copper Test Kit reference colors. (Just remember to calculate the copper concentration reading by the dilution factor).

NOTE: In the case of using Cupramine, the manufacturer, Seachem recommends that at first the amount added is half the final dose. Then later the rest is added to bring the concentration to 0.5ppm. FOLLOW THESE DIRECTIONS. Adding half dose allows the fish to acclimate to the addition of copper. After the second dose totally mixes in, then start the testing for copper.

One advantage of Cupramine is that it is a 14-day treatment AFTER the copper concentration is up into the range (after the second dose). Other medication manufacturers claim their treatment takes longer or shorter, but the 14-day treatment makes sense when you review the life cycle of MI and MV.


DANGER !!! :slap:

Treating with copper cannot be done with many other treatments and medications.

Copper should not be used with any kind of sulfa-based antibiotic.
Never perform a copper treatment in a hyposaline solution. The copper becomes lethal to marine fishes in such a low salt concentration.
Hyposalinity only cures one parasite -- Marine Ich (Cryptocaryon irritans). Copper kills Marine Ich also, so there is no purpose in doing both the copper AND a hyposalinity treatment at the same time (see above).





I hope I've provided some understanding regarding copper treatments.

Post your questions or ask if you would like any elaboration.

[baobao]

Could you please elaborate/clarify the paragraph below? Thanks.

"If you prepare freshly made up saltwater (like you were doing a water change) and test that for copper, you can then use that to dilute your tank sample water for the Salifert Copper test, remembering to account for any copper reading of the freshly prepared water. Thus, you can get the relative accuracy you need from the Salifert Copper Test Kit reference colors. (Just remember to calculate the copper concentration reading by the dilution factor). "

[leebca]

Sure!

Some test kits (for many ingredients in our aquarium) can be used when the concentration of what is being measured is too high for the kit to read. Or, another way of looking at it, the aquarist wants to bring the measurement into the most desirable range of the test kit comparative color chart.

So, to do this the aquarium water sample needs to be diluted. The proper diluent is not tap water, distilled water nor RO/DI water, but freshly made saltwater (FMS) so that the final sample still is saltwater (not diluted saltwater).

To be 'smart' about this, the aquarist makes up some freshly prepared saltwater. In order to verify that the FMS has no copper in it, the FMS is tested with the copper test kit. If it is 'zero' then you have a good diluent (water to dilute the aquarium water sample).

The aquarium water sample is diluted (for example) 1:2 by adding an equal amount of the freshly prepared saltwater to it. Now do the copper test using the mixed FMS and aquarium water. The copper reading should now be in the lower range of the test kit color chart. Take the reading. Double that number since the sample was diluted 1:2. That doubled number is the real concentration of copper in the (undiluted) aquarium water.

If the freshly made saltwater shows a copper reading, then when it is used to dilute the aquarium water sample, that will add copper to the reading. The copper concentration reading of the mix will need adjusting for the copper that was in the FMS.

An example of this (copper measurements are in ppm):
Freshly made saltwater (FMS) read 0.5 copper concentration by the kit;
FMS used to dilute aquarium water 1:2;
Copper from FMS in the mixed/diluted sample is 1/2 of 0.5 or 0.25
Copper test the diluted sample;
Copper measures 0.25 in diluted sample;
Less that which was contributed by the FMS: 0.25 - 0.25 =
The copper concentration in the aquarium water is 0

All this calculation and thought can be avoided if the FMS doesn't contain any measurable copper. If it does, the aquarist should try to figure out where the copper is coming from and stop it.

I included this concept only because it is generally 'good chemistry' practice. The FMS really shouldn't contain any copper in it at all, but the aquarist has to verify that nonetheless.

[weez1959]

Whenever I need to use copper I use Cupramine.

The website/bottle says to add 1/2 on the first day then wait 48 hours for the second dose.

Is there anything wrong with adding it after 24 hours? What if a fish is really covered in ich? Will waiting 48 hours affect the fish' chance of survival.

Would adding the full dose on the same day harm the fish more than help it?

I ask this question because I'm sure there are a few newbies out there wondering the same thing.

Pros and cons, etc...

[leebca]

Louise,

Thanks for asking that question. It is something I rarely cover. This is an area where I and Seachem disagree. Good choice of copper treatment medication. It is, IMHO the best choice.

Seachem has written their instructions to the below-average hobbyist who isn't going to test their water for copper. In my opinion, it is always essential to test the water for copper when performing a copper treatment.

In this respect, I think their directions are a bit misleading and can (and does quite often, I'm afraid) lead to deaths from copper poisoning, or more likely a sub-effective dose of copper being administered.

The original and proper dose of Cupramine is as they state on the bottle/instructions. The target is to bring the copper concentration into the range of close to 0.5 mg/l or 0.5 ppm. The 'guess' by Seachem is that the aquarist will loose much of the copper to carbonate interactions, and thus recommend the second dose.

What I say is that, a few hours after the first dose the copper concentration must be tested to see what has remained in solution. The test kit I use to measure Cupramine is Salifert and Seachem. Most aquarists will find the Seachem Copper Test Kit frustrating to use, so I have found that I get the results I need with the Salifert kit.

These are my instructions:
After the first recommended dose is added, wait 3 hours and test for copper;
Test for copper twice a day;
Add more Cupramine to keep the copper near 0.5 ppm without going over 0.6 ppm, nor under 0.4 ppm;
If dealing with very delicate or copper-sensitive fishes (e.g., tangs), keep the copper concentration at about 0.4 ppm or in the range of 0.3 to 0.5 ppm.

To specifically address your questions (if it wasn't clear from the above):
1. If you add both doses on the same day, you are overdosing copper and the fish can die from copper poisoning.
2. If you add the second dose without checking for copper concentration, you could be adding too much copper or not enough.

Remember how the medication works: Copper only kills the free swimming Cryptocaryon irritans organism. It doesn't affect what is on the fish. So regardless of how covered the fish is with the parasite, adding more copper will not kill any more than it would at the correct concentration. Copper only kills the parasite at a stage the naked human eye can't see the parasite. The value of the copper is to prevent reinfection of the fish by killing the parasite before it can get to infect the fish. It has no affect on the parasite once it's inside/on the fish.

You might want to read some general information on this parasite:
Marine Ich - Myths and Facts

[smpolyp]

Wow!
When YOU have such a great thread YOU not only teach, but raise more questions than one would have before.

[weez1959]

Another question about copper testing, I have both Seachem and Aquarium Pharmaceuticals test kits and I always test when using copper but in a pinch, if you don't have a test on hand and you're using very accurate measuring utensils (I use a 1 ml. syringe in 0.1 graduations, you can get them from a vet for administering meds) and you've carefully measured the water in the QT and you follow the directions on the Seachem website of using 1 ml per 10.5 gallons, wouldn't the chances of overdosing be almost nil? I mention this because when I do test after the first and second addition, I always get the right reading and never overdose. If anything wouldn't underdosing be more of a concern? and if this is the case, would this not be safe for the fish until you can get your hands on a copper test provided it's not more than a day or two without testing?
Phew! that was a long question.
Also, I've heard a few bad reviews on Aquarium Pharmaceuticals tests but I've so far prefered this one to the Seachem test because to me all those blues look the same
Are these tests really that bad, I've been using them for several things, calcium nitrite etc. and comparing to Seachem and Salifert and have found them to be fairly accurate.
I am planning on getting a Salifert copper test (can't have too many) in my next order but is it really that much better the the 2 I've mentioned?

[leebca]

As you reasoned, the most likely scenario is not overdosing, but under dosing. But don't be too kind to the industry, Louise.

Manufacturers have made errors in their products before, recently and most likely will again in the future. The hobby's best defense is awareness and extra checking. This is so easy with the test kits available, for at least this particular ion. Or you could have an instance like I did. I've setup several dozens of FOWLR aquariums in my past. After 6 months maturing, my clean up crew was dying. I had an expert lab do a complete water analysis. It came up 80 ppm copper! I had no idea where it came from, but. . .it was there. I could speculate a few pages on where it may have come from, but such things can and do happen. So what this means is that despite careful, planned additions, something might already be there; the med may be 'off' the source water may be not up to par that day, etc., etc. You and I both have something in common I think, Louise -- we are careful and we don't take chances. The ally for us, here in copper treatment is using the right copper test kit.

Every minute counts, especially with parasites such as Marine Velvet (Amyloodinium ocellatum) that kills so quickly. Keeping the copper in the 'perfect' range -- the effective killing range -- is what is important. Not just too high; but also too low. Is two days a problem? MV can kill in a few hours. How long is too long with this kind of parasite? If the fish is already weakened, MI can kill in a day. How long is too long in this situation?

You use the word 'accuracy' quite often, but in reality the test kits are responding to what they are able to detect. Understand that the color change utilizes some of the copper just to make the color change, so what you read is supposedly 'corrected' to a realistic number. But accurate? Probably not. What they are able to detect and what is actually there can be different. Is this clear? It is a subtlety but a fact in many of our home test kits. The medication contains copper, but that copper, as noted in the first post, can be 'delivered' in different forms. The test kit cannot detect all forms of the copper, but should be able to detect the copper of a particular medicine, provided that the manufacturer has approved the test kit (i.e., knows it will detect the copper in its med).

Using the test kit recommended by the manufacturer is the best way to assure that the copper being measured is the copper that is supposed to be detected is in fact detected. That relates to an acceptance number specified by the medication manufacturer. Is it copper? Not necessarily, if you understand the subtlety noted above.

So rather than 'accuracy' what you're proposing is that the medication copper is detected by another test kit at the similar level that the recommended test kit is detecting it. This is known to me to be true for Cupramine (the medication) and two test kits: Seachem and Salifert Copper test kits. I can't vouch for any others, but would not be surprised to find that others would work -- to various degrees of reliability.

Some test kits use different chemistry to do the detection. In a saltwater aquarium, this makes some more or less reliable. This goes for all sorts of things we test for. Salifert is a reliable set of test kits, priced reasonably, and reasonably easy to use. But I have other favorites for other tests.

Better? Not necessarily. More appropriate for the medication? Yes.

[baobao]

1) what is your experience with precipitation over time using cupramine?
2) I need to lower the ph in my quarantine tank to around 7 to match incoming transcontinental shipment. the qt tank has cupramine at .5 ppm. any advice/caution?

[leebca]

Cupramine resists precipitation probably the best of most meds. However, if the conditions are right, it does complex with plastics, acrylic, carbonates, glass, etc.

I would go ahead and lower the pH and then make a water change (old water lowered pH matching new water lower pH). Since it is a quarantine tank this should be fine. Things gets dicey if the QT has a lot of equipment, or substrate, or rock.

If your QT has carbonates in it, then that is another story and not worth risking further use as is, without thoroughly cleaning. If the QT has filters and equipment, they may need 'rinsing' out with chemicals to remove complexed copper. The safer side would be to use new equipment or equipment never exposed to copper.

[berkdog]

During a fishing quarantine, what reasons would you suggest a copper treatment? For clownfish (Ocellaris), after a freshwater dip and when you start the formalin treatment, would you treat the water with Cupramine (when you have 2-4 more treatments of formalin)?

[leebca]

You're moving toward the wrong direction. The quarantine of fishes is to view them and see if they are infected, not to treat them randomly for parasites or diseases that may or may not be there.

The only reason to treat all Anemonefishes that are exposed to wild fishes or that have come from the wild themselves is because the probability of being infected with Brook is so high. Stop. No reason to go further in any kind of QT treatment on Anemonefishes.

[berkdog]

But even if I buy fish that are raised in a hatchery, you suggest at least the Foramlin treatment because of exposure to other fish at the LFS (exposure to at least the "common" net that catches other fish in the LFS).

Thanks! I think I'm ready to get my first QT fish

[leebca]

Good luck!