I've got nearly 20 years experience in emergency services, including HAZMAT specialist, fire inspector and investigator.
The only way this becomes an issue is if an open flame was exposed to the increased O2 level...the flame would be larger and hotter.
Firearms do produce flames. I've never tested the flame from a firearm and its interaction with medical oxygen being used by the shooter.
If someone were to ask me or if I were called to testify on this i'd say the risk of a larger, hotter flame from the fired weapon is there simply due to the chemistry...its there.
The overall risk would depend on alot of factors; how many liters per minute of O2 is being emitted, % of O2 total in the space (gas monitor), area ventilation, proximity of O2 to flame, etc...
The chance of this resulting in harm is probably very low, but it is there; Chemistry is law. Personally, when i'm old and on O2...i'm still going to the range.