Maybe.I have certainly done my 'shallow' second dive on a rich / optimum mix to flush Nitrogen so that the following morning I can maximise my dive time. [A typical behaviour in Scapa.] Yes, if I avoided the second dive altogether, I would have had more time available than if I did the second dive on an optimum Nitrox mix.
On a long technical dive while doing the final stop on oxygen, if you look at the tissue loading graph on a computer that has one during the last minutes of your final stop, you will see that when you finally go to the surface, during your surface interval, you medium and slow tissues with be off-gassing, as is true for any diving, but your faster tissues will be on-gassing while breathing surface air.
Astronauts and high altitude military pilots breathe pure oxygen for several hours before taking off, hopefully eliminating all oxygen do they can do that fast ascent without getting bent.