Having killed a few buffalo on a farm, I'd say that a brain shot might be the best. I'd also say to aim for the ear, but that might be a really tricky shot with no ear visible to aim for... Unless he's decides on a cow.
Personal thoughts are that if you're going to be backup, a 45-70 with a slow moving heavy hollowpoint might be the best. Or a shotgun with slugs...
The hide of the last bull buffalo I skinned was over an inch and a half thick just behind the ears. He was a juvenile bull. Maybe 650-700 on the rail.
I'd treat bullet selection for them like I was shooting African thick skinned game or cape buffalo.
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