Ah like me a bit of knowledge and dangerous
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Okay as you have a bit of risk management knowledge, what is one factor that often dominates most rules? The lowest common denominator factor. That is rules are often made the person with perhaps the least experience and or knowledge. The person filling cylinders is affectionately known as the fill monkey. While not always appropriate it sets the stage. Now let add in two other factors high pressure gas which can go boom and high percentages of O2 which as Sarah would say burn baby burn (well not quite as we all know that O2 does not burn but is needed for combustion). Each alone are hazmat issues and we are now combining them together.
So while we would like to live in utopia and never have someone fill an unclean cylinder with a high percentage of O2 it can happened. For instance, the O2 monitor is going out and what someone thought was 32% they were banking is actually much higher which just might be enough to cause a problem. Say it will not happen, ever gone in to get a certain percentage of nitrox and gotten some else. Ever had your cylinders accidentally overfilled (not talking a cave-fill) or under filled.
So I suspect, note suspect these reason for the CGA rule staying at 23.5% is for all the dumb azzes out there. I have no proof of that but that would be my educated guess. And I am sure the insurance underwriters have their hand in it as well. While the 40% is fine once mixed and verified. Which again it is my understanding goes back to caissons days when the gas they used were delivered and it was their equipment (not cylinders) that had to be exposed to less than 40%.
Personally, I am rather ambivalent as I have not seen enough evidence. There is reasonable anecdotal evidence that <40% is okay in cylinders but I have not seen counter evidence. Which is really is what is needed. I am sure it out there. How much and to what degree is unknown to me and most. Which is why I have suggested writing GCA/DOT which as a rule making body they would have it.
Like everything "it depends"