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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. The Sidetone function's effect makes it easier to talk using the headphones and helps the headphone microphone pick up sounds and play your voice naturally. 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.