Copper Sticks to Glass - Toss Out Old Tanks

[R Holmes-Farley]

In terms of chemistry of inorganic copper absorption, bare glass is likely to carry a net negative charge in seawater (from silicate) and can bind copper as a copper silicate complex. This is well established in the scientific literature:


Adsorption of some divalent cations from aqueous solution on precipitated silica. Bye, Gerald C.; McEvoy, Michael; Malati, Mounir A. Mid-Kent Coll. Higher Further Educ., Chatham, UK. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases (1983), 79(10), 2311-18.
Abstract

The adsorption of Co2+, Ni2+, Cu2+, Zn2+, and Cd2+ on the K+ form of a pptd. silica is reported. The adsorption isotherms of Co2+ and of Ni2+ at pH 7.0 and different temps. follow the Langmuir isotherm. The endothermic apparent heats of adsorption, 2 and 10 kJ/mol, resp., are compared with those of Cu2+ and Cd2+. The limiting amt. adsorbed, Xm, of the 4 ions decrease as the pH is lowered. An ion-exchange mechanism between hydrated K+ ions in the outer Helmholtz layer and metal, M2+, ions in soln. is proposed. The results also suggest that (MOH)+ ions are adsorbed at the higher pH values. A plot of Xm at pH 6.0 and 323 K for the 5 ions studied against at. no. exhibits the Irving-Williams sequence. At pH 3.0, i.e. close to the point of zero charge of SiO2, the adsorption results were used to calc. the free energy of specific adsorption, DG, using the Grahame equation. The DG values were -11.1, -10.7, -13.4, -13.3, and -12.1 kJ/mol for Co, Ni, Cu, Zn, and Cd, resp. Specific adsorption is tentatively ascribed to the formation of surface coordination complexes.

Ion-exchange adsorption of zinc and copper ions on silica. Kozawa, A. Univ. Nagoya, Japan. Journal of Inorganic and Nuclear Chemistry (1961), 21(3/4), 315-24.
Abstract

Ion-exchange adsorption of Zn and Cu ions on silica were examd. in 2M NH4Cl contg. ZnO or ZnCl2 and in M NH4OAc contg. 0.05M CuCl2, resp. The ion-exchange adsorption attains equil. in about 2 hrs. at 25°. The adsorption of Zn++ increases with the pH of the soln. up to pH 7.12, then decreases. Between pH 5.48 and 6.38 the mole-ratio of H+ released Zn2+ adsorbed is const. at .apprx.3.0. Zn++ adsorption on heated silica decreases markedly with increase in the heating temp. For Cu++ adsorption, the mole-ratio, H+ rel./Cu2+ ads., is 4.0. The infrared absorption spectra of silica samples, heated silica, and silica treated with Zn2+, Cu2+, and Na+ solns., were taken. A decrease in the absorption intensities for the bending vibration of OH groups on the silica is discussed. A surface complex mechanism for metal ion adsorption of silica is proposed; the silica surface is acting as tridentate ligands for the Zn++ adsorption. A new method for detg. the surface acid and the surface area of silica is suggested.



Reaction of silica gel with copper ions in acetate solutions. II. Rak, R. V.; Dushina, A. P.; Aleskovskii, V. B. Leningr. Tekhnol. Inst. im. Lensoveta, Leningrad, USSR. Zhurnal Prikladnoi Khimii (Sankt-Peterburg, Russian Federation) (1971), 44(5), 1068-73.

Abstract

Sorption of Cu ions by silica gel from acetate solns. was studied under 2 different conditions: (a) contact time from 1 min to 24 hr using 4.7 ´ 10-2M Cu(NO3)2 in M AcONa; and (b) contact time from 2 to 120 days with 4.25 ´ 10-4-4.8 ´ 10-2M Cu(NO3)2 in M AcONa. The soly. of the polysilicate salts and the hydrated Cu silicates, in the form of activity products, Kp = aCu2+aSiO32- and Kc = aCu2+aSSiO32-, was (0.8 ± 0.1) ´ 10-19 and 1.9 ´ 10-19, resp.

 

[R Holmes-Farley]

Randy Welcome to Reef Frontiers!!!

Thanks, Brian.

 

[Boomer]

Thanks Randy, more than I expected but then you always try to do more than expected

and

to my new chem forum

 

[Boomer]

One remark My only issue is with this;

Ron Shimek added copper to natural seawater and looked at the effect on sea urchin larvae.

Urchin larave are very, very sensitive to a number of things. It is the reason behind their use in marine biology lab testing. The are often used as toxicty indicators. With that being said, I wish there was more on it, such as fully grown marine shrimp, poly's, ascidians, anemones, etc.. The only info there is can be found here. It will take time to sift through all of it. Make sure you know what kind of animal you are looking at

Go here and type in copper or copper sulfate, etc..



http://preview.pesticideinfo.org/Search_Ecotoxicity.jsp#Chemicals

 

[leebca]

Thanks Randy. Glad to see you could contribute.

May I post your posts at other sites? There are other places where similar discussions are taking place.

It seems that we focus on the copper ion, but with all the other ions around, it seems like it would be in enough competition to really not become a major issue with glass.

Thanks again!

 

[R Holmes-Farley]

May I post your posts at other sites? There are other places where similar discussions are taking place.

Yes, although I already was asked by Ninong to post at his site and I posted it at RC as well.

 

[Ed Hahn]

Randy, This is a Dream. Thanks for visiting and I hope you never leave!

But one more question. How do you feel about people using Muratic acid to clean their empty aquariums?

 

[leebca]

So for me, this means I will wash my old glass tanks that had copper in them first with:
Vinegar, then rinse, then wash with
Soapy water, then rinse, then wash with
Bleach, then rinse, rinse, rinse.

Then it is good enough for a marine tank with invertebrates in it.

 

[R Holmes-Farley]

Muriatic acid is a good way to clean glass. Just dilute it with 10 parts water, and be careful to not get it on yourself.

 

[NaH2O]

Randy - just wanted to Welcome you to Reef Frontiers!!!

 

[Boomer]

Ed

Randy, This is a Dream. Thanks for visiting and I hope you never leave!

I told Randy when I took over this forum to come here any time he wishes and make any comments he wants And that I may be calling on him from time to time for help and to come here.

 

[liveforphysics]

Good to see you here Randy. I have a couple of experiences I will share dealing with psudoreefs and copper. The experiences unfortunately have a bit of contridiction between them, as one suffered no ill effects, and one is still plauged.


This tank was a cichild tank for 18 years prior to me getting it for free and turning it into a reef. The owner kept copper in the water on a regular basis.

The walls of the tank were stained blue/green, as was the substrate and silicone when I got the tank. How the silicone was stained goes against my chem understanding, and i offer no explaination. I do know that it appeared very green/blue, and the hard water deposites were distinctly blue/green.

These are simply my observations.

I washed the tank out with a hose in the lawn, and used a razor blade to remove the extensive hard water deposits. The tank was then filled with tap water. No carbon use. No waterchanges. No skimming. Chaeto and frags are the sole export of this tank.

Now, my 30gal on the other hand was thriving until one of the T5 bulb and connectors droped into the tank running (while I wasnt home) and via electrolisis disolved a large portion of the copper wire and lead/tin solder into the tank. I have performed many massive (~95%) waterchanges in this tank, as well as used huge amounts of carbon over the last few months. This tank had all large inverts die from the initial event, and will still not support coral life in a healthy mannor.


I am certianly not claiming to have any special insight in this area, but I just wanted to contribute my own experiences and obsevations.

I think my next step to try to 'fix' the 30gal will include throwing out and replaceing the substrate and possibly rock as well, along with doing an acid rinse on the tank, followed by a bleach rinse and a through series of flushing the tank out afterwards.


Any/all comments are welcome.

 

[Ed Hahn]

Ed

Randy, This is a Dream. Thanks for visiting and I hope you never leave!

I told Randy when I took over this forum to come here any time he wishes and make any comments he wants And that I may be calling on him from time to time for help and to come here.

Boomer,
Your awesome, and you have a pretty good support team too. I keep begging him to come to Washington, maybe one of these days he will give in.
Thanks for all you do for us hobbyist,
Sincerely,
Ed

 

[Boomer]

Luke

Just to clear things up your post seem like your are talking about 2 tanks, the 18 year old and another 30 gal, is that correct ?

As far as silicon goes I have keep and raised cichild for yeras in a 55 gal and the silicon turned green. This tank does not even know what the word copper, MB or even MG is, never been in the tank. IMHO this is due to lighing and maybe a combo of water, which alters the silicon due to aging. I have googled for a couple of hrs looking fo anything that makes silicon sealant turn green or blue and the is nothing.. aging, deterioration, UV, light exposure, break down, absorption, effect by water and on and on, nothing except comments made on foums and NG groups by aquarium keepers.

 

[liveforphysics]

Boomer- Yes I am talking about 2 tanks. The 55gal that was used by a friends father for cichlids for 18years is the only tank that had the silicone dyed blue/green. Its also the tank in the picture. I do not know what caused the tank and silicone to appear blue/green. You could be correct about UV light or similar effects being related. I just know that when I picked up the free tank, I asked the guy if he used copper, and he said something like "always"... Its always been a healthy tank for me.

The 30gal that I suspect is poisoned by copper(from the bulb dropping into the water incident) shows no indication of blue/green color anywhere. I suspect copper/lead poisoning because before the day the bulb dropped into the tank, it was thriving with life. Currently its basically a FOLR due to corals not being happy in it anymore.

If you have any ideas as to ideas to try that dont involve getting new rock I would love it.

Thanks again
-Luke

 

[Boomer]

Luke

from the bulb dropping into the water incident

I do not buy this kinda, especially with all the water changes, GAC, etc. but then I do not know how much cooper/lead was / is in there and then again maybe it is leaching out of the rocks, would be my best suspect/guess.

You said FOLR. What animals do you see on the LR any or are they dead also. How is the algae growth in this tank ? They do not like copper and lead either. Get a Polyfilter for the fun of it and see it it turns blue.

Seachem USE to make a product that will dissolve all the copper left behind from copper meds and put it back in solution but I do not know how well it really worked. I had it but never tested it. I sent a bunch of stuff to Randy awhile back and I do not remember if it was in the box or not. And if it was, has he played with it or not. The warning on the bottle was "remove all animals first". It does not appear to be made anymore. I can not find it on their website. It was called AntiCopper. 110 ml treated 250-1000 gal. So I'm typing this part for nothing :lol:

 

[liveforphysics]

The wire was completely disolved about 5" up inside the insulation. The end on the bulb was just a waffer skeleton. I had afixed the wire to the bulb directly with solder. There was no traces of solder remaining anywhere.

I think its likely that the bulb dropped into the water as I was dropping back down the canopy in the morning after feeding. When I got home from college and work late that night, the above described scene was what I saw.

The water was white and cloudy. I assume this was due to such a huge amount of biomass that appearently just disolved into the tank (easily +50 coral specimens). I should add that ALL of my snails died (considderable sum), along with my mated CBS pair, and many hermits. The brittle star

Ok, I just took a long look at the 30gal and its 20gal fuge. Thousands of amphipods, and larger shrimp in the sand on both display and fuge. ZERO copepods visible. Many spagetti worms in the fuge, none in the display, possibily due to predidation.

The rocks have a light algae film over them that never used to occur before the incident. It could possibily be a very thin film of blue/green cyno, or some darker diatom variety.

The algae which I use as the nutrient export for this tank appears much darker and thicker than the same strain of chaeto in the tank right across the room from it, and both use the same lighting. The growth rate seems to be slower, but I also cut the feeding rate way back, which could be the explaination.

I took some nutrient measurements, everything still indicated undectable (PO4, NO3 etc) pH 8.1, Ca 380ppm (couldnt seem to find on of the reagent bottles for my alk test).

If I can possibily provide anymore data for you, just let me know. I would love to find some of that anti-copper solution you mentioned. I prepair chem stock solutions for my college on occasion, and if you could give me the composition of the anti-copper solution, I belive I can whip up a batch (assumeing it doenst require some propritary equipment to make).

Thank you very much for your time sir .

-Luke

 

[Boomer]

OK, the I do not buy copper, lead or even mercury ( if the bulb broke). So, I'm am cluelss as to why not corals. I will say this, I have seen this before in a friends tank, kinda, that never had copper. He could keep clams and softies and tha was it, other than things like you menioned, to include urchins and anemones. I always figured that it was his "room air" getting in the tank, due to his nearby wood working shop. His water params, lighting and skimming was perfect.

You are aloud to call Randy Sir on my forum :lol:

 

[liveforphysics]

I think I can safely rule out the room air being a problem. This is a really old (way before the bulb incident) picture, but the tank locations are still the same.

If you are wondering about the 2L bottles, they are the CO2 source for the calcium reactor. Do to its proximity to a very healthy tank, I belive I can safely rule out an enviromental cause.

Also, an enviromental cause wouldn't explain why everything went nuclear after the bulb dropped in.

I'm currently in the process of moving, and I'm thinking about just giving away that whole setup to somebody who wants to use it for freshwater or FOLR, unless you or someone can think of something new to try out in hopes to cure its curse.


Its great that you have your own forum here, I think you will like it.

 

[R Holmes-Farley]

Seachem USE to make a product that will dissolve all the copper left behind from copper meds and put it back in solution but I do not know how well it really worked.

Maybe it was the "amine" ligands from their cupramine product.