You can survive on a variety of mixes - those figures are overall numbers; they change with altitude for a start. Divers use weird mixes because the pressure affects how they absorb it, and then there's the obvious use of oxygen-enriched air in medicine and stuff like jet fighters. Really high concentrations can lead to stuff like oxygen toxicity, but a boost of a few percent should be fine. The body would tune the lung function and red blood cell count to get the right amount, so you'd feel weak for a bit if you switched back to normal, like altitude sickness.