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it is usually an overdose of an injectable anasthetic. much the same method used by vets.
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One drug used in Switzerland, Oregon in the USA and Belgium, is Pentobarbital. http://www.lifenews.com/bio2383.html
On the BBC program with Julie Walters it was barbiturates but these are not always so instantaneous as the program showed according to the attached link http://74.125.77.132/search?q=cache:MjDp09FPobMJ:www.pccef.org/articles/TheoryVS...