Yesterday, I played around with what I had a bit more - that is, I restarted it, re-set it up with the same settings, modified a few based on (_ANSYS Customer Portal_Training Materials_eulerian_multiphase_granular) and, amazingly, finally got mixing occuring.
"OK. Assuming the calcium is a "fluid" rather than a disolving solid make a multibody part (DesignModeler) or use ShareTopology (SpaceClaim) to get a conformal mesh. Label the volumes to suit. Then in Fluent you patch in the materials."
Bold is what I had. I patched the calcium into the calcium cuboid at 0.5 Volume Fraction.
It took me 40-60 hours to get the ropes on DesignModeler over the past few months (comfortable enough that I can make the complex shapes I'm currently working on; the complexity of the actual model relative to my DesignModeler skills was why I had to go so simple at the start); SpaceClaim would be another big time sink.
Thanks for your help, genuinely much appreciated.