Yes, my post above was a direct response to the announcement email (which was cross-posted to Ambassadors)! The announcement linked to this page and not everybody over there was interested in the IRC meetings so I replied over here instead.
If we make it common for people to ask questions on Ambassadors, the technology is very different but the workflow is similar. On IRC, what typically happens is that when a volunteer comes in to ask a question, the hosts would start looking for the person who knows the answer, then the answerer will discuss the problem with the asker on the IRC channel.
This would not be so different with a mailing list workflow: someone can ask a question, the staff devs will look for someone who can answer the question, and the answerer can reply either on-list or off-list depending on whether they think the question will be of interest to many people. Socially I think it's the same workflow.