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people paint thier pvc pipe that goes in the water so i don't see why not. i think krylon fusion is what is best to use. I would be more worried about it flaking off and fish eating it than it poisoning your water.
Just a bit of info on the Krylon Fusion... it actually bonds to the plastic (if sprayed on plastic) which helps make it tank safe (I use it all the time on plastic stuff for my reef tank). Im not sure if you would get the same "bonding" if spraying it on rock.
I guess you could also say that once the paint is cured... the paint itself wont be a problem, only it flaking off of the rock would become the problem.
you might want to research concrete stains....don't know if they are safe or not, but it should work. Also RIT dyes (if you can remember tye-dying shirts) may work, but I don't know about toxicity with fish...good luck!
215g Malawi Peacocks and Mbuna
180g Tropheus Ikola and Bemba and Clown Loaches
58g Bristlenose breeding and grow out
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