To get 100k miles on front pads is not unusual. I got 130k miles out of the front pads on my wife's Outback. But rear pads usually need replacement before 100k miles. Of course brake life differs greatly, depending on factors such as driving style, vehicle weight and quality of brake pads
Depending upon how many miles your wife drives each month, and how aggressive of a driver she is, will make a difference on the urgency you put into having pads replaced. Generally, 4 mm is considered a still safe and usable amount of pad. Plenty of material between the rotor and the pad backing plate. But if you are one to forget to watch maintenance items on a car, then I would replace them at 4 mm. If your brake pads are measuring 3 mm or below, start planning on getting them replaced soon. At 2 mm, get it scheduled immediately.
For reference, some states and countries where safety inspections are mandatory, will fail a vehicle at 1.5 mm.