I was thinking about this as well but concluded she wasn't for the same reasons stated above. But in that case I wonder what happened to the WSC after everything that unfolded in TWS.
Black Widow was always the WSC woman, even when she was riding that Chitauri sled or using Loki's sceptre to stop the invasion. During that time she slipped on that mask and spoke to Nick Fury and tried to prevent him from actually helping the Avengers while they were fighting in NYC. The reason she asks Cap to give her a boost up to that Chitauri sled is so that Cap won't see her putting on the mask when she's up there in mid flight. She actually put it on while back flipping.
The Chitauri were naturally distracted because they wondered why Jenny Agutter was on a sky sled and recalled they saw her boobs in the movie "Walkabout" when researching earth footage prior to their invasion.
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