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I posted this over on a different forum regarding this topic:
Don't ever pay for Nitrogen filling. Air is ~78% Nitrogen. *IF* Nitrogen was "bigger" and leaked out more slowly than "air," over time, everything except that 78% N would leak out. So then, your tires would be 78% full pressure, but 100% full of N. Pump 'em up with air again, and you're adding 78% Nitrogen again, to give you 95% N (78% + (78% of 22% = 17%). So after two fills with air, you'd be at 95% N. A third fill would bring it to 99%.
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