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Just making sure I'm reading this right. From Codex Witch Hunters:

In missions where there is a choice of table edge, the Inquisitor must take a Leadership test before the game and if this is passed he may choose the deployment zone for his army rather than rolling a dice for it.

So if you combine this with a 5th Edition mission, then you could conceivably roll a LD10 test to take deployment zone and first turn instead of a straight d6 roll off?

No. How it works is clearly answered in the Codex Witch Hunters FAQ.