For me, i've never had to euthanise large fish, the only fish i've ever had to euthanise are fish like neons, guppys, platys and a molly once etc- basically small fish.
I have always found that putting the fish in a freezing bowl of water is a humane form of euthanasia (i.e. fish does not appear to suffer much, and dies very quickly, within seconds) and has always worked with 100% success for me.
This is the way i go about it;
a. Put plastic/ceramic/glass etc bowl with about 2-3inches of water in it in freezer.
b. Allow water to freeze enough to form a thin layer of ice completely covering the surface of the water.
c. Take bowl out of freezer and break the ice on the surface of the water.
d. Net sick fish and put it in bowl of water and watch it and wait for it to die.
e. Remove dead fish and wrap it in tissue paper and then dispose of it (bury it or put it in bin etc).
I've had to ethunise many fish during the years i have been fishkeeping, most of the fish i have had to euthanise were during certain moments in my fishkeeping experience, mostly during when i had a couple of outbreaks of fish tb and NTD (both untreatable and lethal/nasty fish diseases).
I've also had to euthanise fish dying from old age, like my old female molly, when she reached the grand old molly age of just over 4years old (the maximum average life expectancy for mollys), her health went down hill a lot, she gradually stopped eating and being active and ended up getting a swimbladder problem in the last week or so of her life as she lost a lot of body weight. I knew that she wasn't going to get better and her body wasn't coping anymore due to her age, so i euthanised her with the freezing water method when i knew she was in a bad way and was not going to get better. She died very quickly with this method.
So i would say i'm very experienced with the freezing water method of euthanasia on small fish. I've watched small tropical fish die with this method each time i've used it- what happens is that the fish hovers in the water for a few moments, then dashes around once or twice and then dies seconds after that. I watch the fish for fin, mouth and gill movements. Even though i know the fish is dead (its never taken more than about 20 or so seconds tops for fish to die with this method for me, i define "dead" being when the fish is no longer breathing or moving), i leave it in the water for a further minute or so to make sure there is absolutely no chance of the fish revieving.
You are never really going to be able to kill the fish absolutely instantainously, neither can you do the same with human beings. With human beings, i have read stories that when humans have been decapitated, it can take minutes before the brain is well and truly dead.
I think the fish dying in 30 seconds or less with the fish displaying little signs of stress or pain is a sign of a humane death.
The freezing method is always going to work best on small tropical fish. On sub-tropical or coldwater fish, it probably wouldn't work as well, and certainly not on fish larger than 3inches long.
My question, is that what are the most humane methods of euthanisa on large fish (particularly tough ones like large plecos)? I hate to think about anything bad happening to any of my plecos, but what if (imaginary scenario) one of my large plecos contracted an lethal and untreatable and nasty disease and had to be euthanised, what would you people do in such a situation? There are plenty of forms of euthanisia that work very well on small tropical fish, but not that many good methods for large ones.