To me, the red and blue curves part company around 1995.

1995 is the year the Internet went mainstream.
The first Netscape browser was released.
Microsoft released their Windows 95 operating system.
These two events revolutionized the way business did business.
Documents no loger had to be Fed Ex'ed overnight. They could be emailed. People could start chatting online. Less need to drive and fly to every meeting.

Maybe the Internet is the bigger reason why big red is trending down?

Interesting point. My impression is telecommuting isn't really much of a factor - not many people, not many days, usually give it up before long. I wouldn't expect the changes in freight delivery to have much impact since trucks are a small fraction of total miles. The lines definitely look a little different in the last decade. However, one can also argue the era after 1991 or so is a long period with no oil shocks, and that might have to do with it. Not saying you're wrong, but hard to tell.

It seems useful to investigate aviation - it's transactions and economic activity, but removes the land use factors that seem like they'd come into play a lot in the highway mileage.

We switched from direct flight to hub and spoke systems and milage went up for air flights. We could switch back if jet fuel prices went up again. More aircraft, more crew, more routes, less time in the air, at higher ticket prices.
Good point.
Transportation Energy Data Book says that aviation passenger miles grew at 4.8% annually from 1970- 2002 (ie significantly faster than GDP), but it was only 2.9% from 1992-2002 (pretty similar to GDP). I guess the earlier part of the curve was very much still in the adoption phase for airline traffic, and now maybe it has settled down to be similar to GDP.