What is the ruling on performing voluntary prayers during official working hours?

All perfect praise be to Allah, The Lord of The Worlds, and may His Peace and Blessings be upon our Prophet Muhammad and upon all of his family and companions

There is no harm if  there was break time during official working hours, but if not then it is impermissible. And Allah Knows Best.

Is it permissible for a man to marry up to four wives (polygamy in Islam) for pleasure although he can`t afford that?

It is desirable for the man to have one wife if there was no need for him to have more, if he can't afford marriage forthcoming expenses.

What is the Sharia (Islamic law) ruling on masturbation?

According to trustful physicians, masturbation is harmful to one`s health, and is forbidden according to the majority of Muslim scholars. Therefore, a Muslim should avoid all that which inflicts harm on him in the life of this world and the Hereafter.

Should a pregnant woman who broke fast because of pregnancy make it up, and is a ransom due on her?

The pregnant and the suckling, if they fear for their health, may break their fast and make up for it, and no ransom is due on them. However, if they broke fast in fear for the fetus and the baby, then they are obliged to make up for it, and pay the ransom which is feeding a needy person for each of the missed fasting days. And Allah Knows Best.