a. 3d 
The electrons in an atom fill the shells in order from least energy to higher energy. The orbitals from lowest to highest are
 1s - 1 orbital, 2 electrons
 2s - 1 orbital, 2 electrons
 2p - 3 orbitals, 6 electrons
 3s - 1 orbital, 2 electrons
 3p - 3 orbitals, 6 electrons.
 4s - 1 orbital, 2 electrons. Note the energy for the 4s orbital is just barely 
lower than the 3d orbitals. So it fills up before the 3d orbitals.
 3d - 5 orbitals, 10 electrons.
 
 Since the 20th electron fills the 4s shell, the 21st electron goes into the next higher energy orbital which is one of the 3d orbitals.