I completely agree with you. We have tests like that done with styrene a couple times a year. According to the hygienist that conducts the tests, the acetone and styrene interfere with each other. The acetone artificially hikes up the measured quantities of styrene, we are borderline but still under. That's why I'm looking for a theoretical approach. I want to use the theoretical results to see if further and more controlled testing is required. For example, if the theoretical results are half of the PEL, then I'll feel good saying my workers are safe (for acetone at least) but if the theoretical results are 10% under, then I'll look for a more controlled test.
I hope that explains my situation a little more.