If someone is a volunteer at a company or a governmental agency and they want to ask about opportunities for paid positions how can they get up the courage to do so?

I was in a similar situation during my internship and what worked best for me was simply asking a trusted person who dealt with the hiring! If you don't feel comfortable with that, you can also contact the Human Resources department of the organization to see about available positions and ask someone from your department for a letter of recommendation.

In addition to the above, the people that you work with will be your best to advocate for you when the organization has open positions but you have to let them know first so that they can propose your name when those discussions come up.

You can also ask to split your volunteer time between your current department and the department that has open job positions to get some insight on the type of work involved and get some experience at the same time.

All the best.

If you don't ask, you won't get the opportunity! Often organizations have internal job boards or otherwise share job postings. If you let your mentor/supervisor/colleagues at the organizations know you are interested in employment opportunities, and to let you know if they hear of anything, that will go a long way to get in the door. Best of luck!