[Ninong]

Originally Posted by cichlidfort

Wait...now your saying it takes slow effects for some inverts?

I don't know what you mean by "now you're saying." I have said that copper in the low ppb range, as low as 1-5 ppb, can be toxic to some invertebrates, especially mollusks and polychaetes. Greenbean pointed out that even for invertebrates that may not exhibit acute symptoms right way, the deteterious effects are cumulative resulting in chronic poisoning that may take a relatively long period to develop.

Some inverts are affected almost immediately and others may not exhibit the harmful effects until later on.

Instead of just pulling up articles form Dr. Randy Holmes-Farley, why can't you explain it yourself?

I have already explained it myself, more than once. You seem to think that the fact that copper is adsorbed onto glass "sounds ridiculous." I believe you said the same thing about copper being adsorbed onto live rock. I don't believe we share sufficient common ground to carry on a reasonable discussion.

Not trying to be rude or anything, I just want a debate, not a contest to see who can pull up the most convincing articles.

There is nothing to debate. You are free to believe whatever you choose. If you choose to read the following comments that I lifted from the E.P.A., you may wish to ignore that opening sentence where they mention the fact that copper strongly adsorbs to carbonates, something you said "is ridiculous." Live rock is calcium carbonate. Feel free to ignore references to "chronic toxicity" and the claim that "copper will bioconcentrate in many different organs in fish and mollusks." In particular, pay no attention to the statement that "there is low potential for bioconcentration in fish, but high potential in mollusks" because that is exactly what I have been saying since the beginning of this thread.

Toxicity Profiles:

Copper

Copper is a micronutrient and toxin. It strongly adsorbs to organic matter, carbonates and clay, which reduces its bioavailability. Copper is highly toxic in aquatic environments and has effects in fish, invertebrates, and amphibians, with all three groups equally sensitive to chronic toxicity (USEPA 1993; Horne and Dunson 1995). Copper is highly toxic to amphibians (including mortality and sodium loss), with adverse effects in tadpoles and embryos (Horne and Dunson 1995; Owen 1981). Copper will bioconcentrate in many different organs in fish and mollusks (Owen 1981). There is low potential for bioconcentration in fish, but high potential in mollusks. Copper sulfate and other copper compounds are effective algaecides (free copper ions are the lethal agent). Single-cell and filamentous algae and cyanobacteria are particularly susceptible to the acute effects, which include reductions in photosynthesis and growth, loss of photosynthetic pigments, disruption of potassium regulation, and mortality. Sensitive algae may be affected by free copper at low (parts per billion) ppb concentrations in freshwater.

There is a moderate potential for bioaccumulation in plants and no biomagnification.Toxic effects in birds include reduced growth rates, lowered egg production, and developmental abnormalities. While mammals are not as sensitive to copper toxicity as aquatic organisms, toxicity in mammals includes a wide range of animals and effects such as liver cirrhosis, necrosis in kidneys and the brain, gastrointestinal distress, lesions, low blood pressure, and fetal mortality. (ATSDR 1990c; Kabata-Pendias and Pendias 1992; Ware 1983; Vymazal 1995).


Additional information from:
Kenneth M. Brooks, Ph.D.

Aquatic Environmental Sciences
644 Old Eaglemount Road
Port Townsend, WA 98368


Copper is clearly the metal of most concern in both fresh water and marine environments. From a purely biological point of view, the cupric ion should be maintained below 6 ppb in marine environments. Either the EPA limit of 2.9 ppb, or the Washington State marine standard of 2.5 ppb appear adequate to protect marine life.

His study is mainly concerned with freshwater fish, although salmon live most of their lives in seawater. Here are a few selected quotes:

These studies suggest that coho salmon and rainbow trout (two species in the genus Oncorhynchus) will avoid areas with copper levels elevated above 4.4 ppb and therefore avoid the stress associated with low levels of copper exposure.


McPherson (1976) reported impaired migratory ability at copper levels as low as 5 ppb in coho salmon (Oncorhynchus kisutch).


There are many sites online that give data on copper toxicity to various marine taxa, but I think any further references at this point are unnecessary. Either one accepts the fact that copper in the low ppb range is toxic to marine biota or one doesn't.

For what it's worth, I will post a few typical comments from the advice section of Robert Fenner's www.wetwebmedia.com site:

Question: My question is in regards to copper use in a fish and live rock tank. I had an outbreak of ick a little while back and my LFS gave me some sea cure and told me to put it in my tank as directed. Since then I have discovered that that was not a good idea. Have I completely ruin my live rock and sand? I really want to get a nice coralline covering. Is this still possible or should I start over? I know that the website said that my tank would never be suitable for invertebrates after copper use.

Answer: Afraid so.

Q: I would really like to have some snails and cleaner shrimp. I am in desperate need of some GOOD information.

A: I think it is time to 'fire' this LFS and find another! Using the rock/tank for fish only tank would be OK after removable of all copper in the water column. Use Poly-Filter and carbon and a good test kit to confirm.


Copper and Live Rock
Dear Bob,

<Anthony Calfo in your service>

Q: I wrote to you before regarding my problem with white spot in my tank. I was advised to use MarinOomed which I did to no avail so I used copper and this has worked wonders. Before the use of the copper all my fish had died but I made the mistake of not taking out the live rock so all the life and algae has died on that too. I now have a powder brown tang and a juvenile Koran angel fish in there and they are both doing excellent. The colours are the best I have ever seen!! My Question is that will the live rock eventually get life into it and will the algae start to grow again if I just leave it or do I have to replace it?

A: That depends on your goals and purpose for the live rock. If it's presence is mostly or only biological for a fish only tank, then you may leave it. If you have any hope of putting inverts in there (or going reef) then the rock must be replaced. Copper chemically binds with all calcareous media (sand, gravel, shell, rock) and will contaminate some inverts on contact even when copper is free from the water column.

Q: Also all the parameters are great now to so should I just leave it for nature to take its course or have I already lost the battle and no life will ever grow on the rocks? PS. I have carbon in there also and am told this will remove the copper in time.

A: The carbon absolutely will not remove copper, but a Polyfilter (Poly Bio Marine) will help. Life forms including beneficial algae will certainly return in time... just not all forms that you had previously. Avoid even putting snails or anemones with this rock in the future for the above reasons.

Kind regards, Anthony


More Live Rock/Copper
Mr. Fenner:

<Anthony Calfo in your service with the follow up>

Q: Thanks for the response. However, I do have a few questions on your answers. You indicated it has attached to all of the substrate in the tank live rock, coral gravel, etc..

A: Yes...chemically bound to all calcareous media even when water tests copper free.

Q: After I make sure all of the copper is gone, If I add new live rock will it survive?

A: Significant copper will not be imparted to the new rock...but the old rock/sand/shells/etc is still a problem.

Q: Secondly, can I use the now copper treated rock as base rock or do I throw it away.

A: Fine for fish only systems...but never with invertebrates that can attach or crawl over it (starfish, anemones, coral, etc).

Q: Do I throw the crushed coral gravel away as well and my colored hard corals that made my wife so appreciative of the tank?

A: The crushed coral will be cheaper to replace than neutralize... I'll have to ask around for a refresher on how to chemically liberate the copper adsorbed on your curios so they are not wasted.

Q: Thank you again for your assistance. I did my reading before hand however I relied upon the LFS for backup and I felt he had more experience than I. I guess I had the correct answer and he did not, but I lost the battle hopefully not the war.

A: Agreed...kind regards, Anthony.


Q: can i use copper in a tank with live rocks? if not what can be used?

A: Uh, no, not really... many of the live rock organisms will be killed... and the copper would be readily absorbed... and regarding the second question...what are you intending to use the copper for?

Bob Fenner


Live Rock & Copper
Q: Is live rock, when used in a quarantine tank with CopperSafe to treat marine ich, still "live"? Or does the copper kill off all the little critters in the live rock, essentially turning it into inert but porous rock? Once your copper treatments have been completed, does restoring the live rock to freshly made salt water, without copper, restore its live qualities? (if they were ever gone...?)

A: NO! The calcium carbonate the rock is principally made from fixes and absorbs the copper making the rock unsafe for further use with invertebrates, etc.

Craig


Q: I am using a stainless steel mesh in the system and I notice it started rusting about 1 week back.

A: GET THAT OUT NOW! God only knows what metals are leaching into the system. You need to find a Polyfilter or equivalent product and use it right away, this can pull a lot of the toxins out of your tank. See if you can find a copper test kit and check your water. If you have had copper contamination, then your tank is permanently hostile to inverts. Time to start over if that's the case.

Q: I cannot think of anything that causes the death of my shrimps.. I have not add anything to the system.. is it the rust? If yes, can I still keep shrimps in the future? Does the rust change anything in the water? My worm and fishes are still doing fine after 4 days my shrimps died.

A: I think I already answered that one. Hopefully there's been no copper leached into your system.


Q: I am slowly trying to convert my 155L tank to a reef system by firstly adding small amounts of live rock each month. I started this wonderful hobby in December 04 and had a case of ich (February) and was foolishly advised to treat with copper in my display tank by my LFS which worked.

A: Well... good for the fish!

Q: I have performed numerous water changes to reduce the level of copper in the system and thought about taking out the substrate and adding live sand with a large water change to eliminate all the copper readings (which are low 0.01-0.02). Can I add cured live sand straight into my tank and will it survive?

A: I'd try to remove even more copper by the use of absorptive media such as Poly Filter, which changes color to show that it's absorbing the copper.

Q: Will treating the tank previously with copper reduce the chance of successfully running a reef system?

A: Well, Brad, copper will continue to leach from substrate, rocks, and the tank itself over time, but the continued use of the aforementioned absorptive media and regular frequent water changes should help dilute the remaining copper to even lower levels. I'd employ these methods for several weeks, then, after continued water testing indicates undetectable copper levels, begin slow and judicious stocking of invertebrates in the system. Proceed with caution. Good luck!

P.S. -- I don't agree fully with that last bit of advice. I don't believe the tank will be 100% safe for all invertebrates after only a few weeks of running polyfilters. Polyfilters cannot remove adsorbed copper. They can only remove the copper as it is released over time. It could continue to leach copper for many months, even years, and this will not be picked up by copper test kits. The test kits cannot measure copper that is adsorbed and none of the test kits can measure copper in the low ppb range. It is OK to use such a tank as a fish-only tank but I wouldn't want to use it as a reef tank unless it had been properly decontaminated with hydrochloric or nitric acid wash, followed by rinses with distilled water, followed by an acetone wash and then several rinses with either distilled or R.O./D.I. water.

Furthermore, the makers of polyfilters, Poly-Bio-Marine, claim that their polyfilters will NOT remove ALL copper. Their filters are incapable of removing copper below ~30 ppb. That's just not good enough. That level would be capable of chronic toxicity for many invertebrates. Dr. Randy Holmes-Farley discusses the polyfilter issue in this thread on Reef Central. In reviewing the manufacturer's website, I found a statement that their polyfilter is designed so as NOT to remove all trace elements. I also found a claim that they had removed copper down to 40 ppb and that they considered that level acceptable for invertebrates. Well, they're wrong! Obviously the invertebrates didn't die right away, so they jumped to the incorrect conclusion that 40 ppb Cu was an acceptable level. It's not! They didn't bother to describe exactly what "invertebrates" they employed to test their 40 ppb Cu hypothesis.