If I'm not mistaken, a copper union would probably be one that has sweat fittings for soldering. A brass union would be threaded.
The reason for this is brass, being a copper alloy, is a bit harder than pure copper, about twice as hard on the Brinell scale. Thus it can take threads a lot more robustly than copper.
So, if you want to re-use the fitting or are working with threaded pipe, etc. brass may be called for. If minimizing your work, use a copper sweat union.