Any hours that you work above 40 hours in a pay period, will be calculated at an overtime rate. However, the shift that counts towards overtime is based on which shift was last confirmed in that pay period.
For example: A nurse gets confirmed for shifts on Sunday, Monday, Wednesday, Thursday, and Saturday in a single pay period. These would all be regular hours worked. However, the nurse then gets confirmed for a shift on Tuesday during the same pay period. Since this shift was the last to be confirmed, this is the shift that would count towards overtime.