Laura, I have one suggestion, speaking from own experience in taking on
volunteers.

In a former position, I found that people who called expressing interest in
volunteering were often told exactly what you were told.
That is, they were told they could volunteer in the gift shop or at the
reception desk.

At the time, I was registrar, and I *really* wanted and needed good,
interested volunteers, especially ones with a background such as yours, who
were looking for specific experience.  It was not a museum policy that
limited where volunteers could work, simply that whoever had answered the
phone that day did not know I would have loved a volunteer such as
yourself.

Perhaps you might try phoning the registration/collection management
department directly, sending your CV along in advance of the call.  I would
think that would be worth a shot.

Good luck!

Barbra Brady
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