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During a call on the headphones, the headphones' microphones pick up the ambient sound regardless of the Ambient Sound Control function setting. This is an effect of the Sidetone function, that enables your voice to be heard naturally, and that makes it more comfortable to talk during the call. As a result, the noise canceling function works differently from when playing music.
If you hear ambient sound, headphones operation sound, or white noise (a small electrical noise with continuous static sound) from the headphones, that is also an effect of the Sidetone function, not a malfunction.