  The set of doubly-stochastic quantum channels and its subset of mixtures of
unitaries are investigated. We provide a detailed analysis of their structure
together with computable criteria for the separation of the two sets. When
applied to O(d)-covariant channels this leads to a complete characterization
and reveals a remarkable feature: instances of channels which are not in the
convex hull of unitaries can return to it when either taking finitely many
copies of them or supplementing with a completely depolarizing channel. In
these scenarios this implies that a channel whose noise initially resists any
environment-assisted attempt of correction can become perfectly correctable.
