Still confused, does this help? Note, this ticket was booked through a Lufthansa agent on the phone.

Way there:
AC 7522 operated by: AIR CANADA EXPRESS - SKY REGIONAL
LH 5525 operated by: AIR CANADA

Way back:
LH 2037 operated by: LUFTHANSA
LH 474 operated by: LUFTHANSA
AC 7527 operated by: AIR CANADA EXPRESS - SKY REGIONAL

So, with this in mind, which segments will I be able to apply my Aeroplan to?
And, for any segments not elegible for Aeroplan, should I enrol in Miles and More?

Thanks all!