Really we need a test that is unlimited in the number of VOCs potentially present in humans, my guess is especially sulfides, amines, methyls etc. None of these are currently tested for, but probably could be.
It may turn out that testing in the urine does not give the full picture, and that some of the VOCs will have already dissipated in the blood before reaching the urine.
Whatever, that is the way to go. My guess is that NMR testing would be most suited for this, by I am not knowledgeable enough to be sure.
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