Warhammer The Relentless,
You can calibrate with any known source--air, even in Mississippi--is a known source. However, for nearly every measuring device known to man, it is better to calibrate it with something that is about the same as what you are measuring. This is because most properties and/or measuring devices are not completely linear.
I am not expert on how critical it is to know whether your O2 is 34% or 32%, but if it is critical, it would be best to use a sample in the range that you want to measure. Oh yeah, and remember what I wrote a long time ago about air samples--do not take them close to stack or other device that might be richer in CO2, etc.
Okay?
Joewr