Someone wiped over his shoes after wearing them in a state of purity, then took them off and prayed without them?
Ablution is not invalidated by taking off leather socks or shoes after wiping over them. However, whoever takes them off after wiping must wash his feet only. If he prayed without washing his feet, he must wash his feet and repeat the prayer. And Allah the Almighty knows best.
What is the ruling on wiping the head during ablution from behind a barrier like a headscarf (hijab)?
The obligation in ablution is to wipe some of the head; it is not a condition to wipe all of it. As for one who has a turban or headscarf on their head, it is permissible for them to wipe over it after wiping a part of their head in any place. This is easily done at the front of the head. This means the woman begins by wiping the front of her head from under the headscarf, then completes the wiping to the back of the head from over the headscarf. If the woman wipes over the headscarf on her head and the moisture reaches the scalp or some hair within the boundaries of the head, it suffices for wiping the head. And Allah the Almighty knows best.
What is the ruling on water present on the floor of a toilet/bathroom?
The default ruling is the purity of this water present on the bathroom floor. If one is certain or strongly suspects its impurity, then one washes whatever part of the body or clothing this impure water has touched. If one doubts its impurity, the default is purity, and we do not rule it impure based on mere doubt. And Allah the Almighty knows best.
What is the ruling on ablution if vaginal discharge is expelled, and is it impure?
If these discharges exit from the external genitalia (apparent part of the vagina), they are not impure and do not invalidate ablution. If they exit from the internal part, they are impure and do invalidate ablution. If it is uncertain whether they are from the internal or external part, they are not impure and do not invalidate ablution.
The apparent part is what becomes visible when sitting, and what the husband's penis reaches during intercourse is considered part of the apparent. The internal part is what is beyond that. And Allah the Almighty knows best.