You can double tap the home button, swipe (left to right) twice to bring up the volume slider and airplay icon. You will also see it within apps that are compatible. Make sure airplay is turned on in ATV settings and that both are on the same network. Ensure the iPod and ATV are is up to date.
Note: audio is on by default but not all will be enabled for video, which is up to the developer to do.
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