Is it legal to use a pellet rifle for dispatching furbearers?
Yes,
Obviously a .22 to the head is the preferred, but are there any animals where a headshot isn't ideal, where it might bring down the price of the pelt?
Just a curiosity?
Larger animals a .22 to the head is humane and does no damage. Some places such as no shooting zones you cannot use this method. There are also some animals such as mink, skunks, muskrats that shooting an animal typically causes too much damage. In both cases the recommended method of dispatch is gassing with CO2.
You need a tub with lid large enough to contain the trap and a Cannister of CO2 available at a welding supply. CO2 is heavier then air so you fill the tub with CO2 displacing the air. Odorless and colorless the animal continues to breath until it passes out. Some mixing with air may occur so usually you have to overfill a little.
Of course none of this is neccesary when using lethal traps which are commonly used on smaller animals.
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