The correct option is A At its peak, the Pony Express employed over 180 riders who ranged in age from 11 to 50 years old, and earned $50 a month.
The use of 'largest', though not grammatically incorrect, seems a bit inappropriate. The sentence means to talk about how the Pony Express employed a lot riders who were paid for their services when it was at its highest point. In this context, option D is the only choice that fits in perfectly. The rest of the option either do not convey this meaning or state something out of context.