This is what I said on this subject on one of the Newsgroups recently, after I consulted with an expert fish vet:
I consulted with a specialist vet recently and I discussed euthanasia with him. He said (I quote):
"Well, you can use a method that is pretty but cruel, or ugly but kind".
He said that a twack over the head, or dropping into boiling water (if it's a very small fish who's brain won't realise it's being boiled until it is unconscious - such as a pencilfish or neon tetra
not a goldfish or bigger fish). Such methods cause instantaneous brain-death, and therefore little or no suffering.
Seeing as fish live in water anaesthetic over-dose doesn't really work (anaesthetic is oil-soluble and simply poisons the fish without killing it - which is nasty). That is even taking into account that a fish is pretty difficult to inject (and catching it and injecting it causes considerable suffering). You cannot use a ether box because ether is not water soluble and all that would happen is that the fish would suffocate due to lack of oxygen.
Poisoning the fish (by use of drugs or poisons) causes definite distress and things like swelling of the gills, that chokes the fish to death - slowly. This applies also to injectable anaesthetics over-doses, as you'd use for a dog or cat.
Exposing the fish to the air causes the fish terror and leads to collapsed gills and suffocation (like death by drowning - also not a nice way to go).
Freezing alive (which is commonly recommended) causes the fish the suffering of frost-bite long before it goes unconscious. This can be counteracted by making the fish unconscious first, but since you cannot use anaethetics (as I've just explained) the vet told me that there is evidence that most of these methods cause suffering (such as putting the fish in CO2). The alka-selzer method *might* be humane, but personally I tried it and I'm not convinced - the fish struggled for 15 minutes in a most distressing way
Flushing the fish alive down the toilet is absolutely barbaric, IMHO, and even worse than "drowing" the fish by taking it out of water. The fish basically gets burned with poisons and suffocated in sewage. It's also illegal in many areas to dispose of "livestock" via the public sewer system.
Slowly cooling the fish, by turning off the heater and then placing the fish in a bag of water in the fridge, is probably humane, albeit slow. It causes the fish to gradually go into hypothermic sleep, without frostbite. Once the fish is asleep, freezing to death is not cruel, as far as the vet believes. The bag must be set up correctly, with 2/3rds more air than water, just as you would do for transportation, and should
be kept wrapped in newspaper to keep the fish in the dark and therefore calm. It is however emotionally difficult for the owner (I couldn't do it).
So, although this is something caring pet owners never want to think about, it is worth considering how you'd do it if a
fish really needed euthanasia. I would personally rather keep a fish in it's own tank and spend a fortune on medications than give up at the first hurdle, but if you are responsible, you cannot allow an obviously unsalvageable animal suffer.