PIK I would see as being quite likely at some point if not soon. LBA would only happen with and extra based aircraft or an LBA base. If they were adding an aircraft and a route, I'd have thought Charleroi or Hahn would be more profitable. Add to that that they'll be starting SNN-LBA in November and won't want to put unnecessary pressure on a new route and I'd be surprised to see it. Then again Ryanair have a history of surprising me!
As regards Madrid... It suffers from lack of two-way traffic, which almost all the other city break destinations have. Amsterdam, Berlin and Paris carry a lot of tourists into Ireland, while Prague and Budapest have the support of immigrant communities. The bucket and spade routes can generally sustain themselves (over the summer at least) with Irish passengers only. Without the inbound passengers, Madrid probably needed an Iberia code-share and with Aer Lingus out of one world and no longer code-sharing out of Dublin, that wasn't ever likely to happen.