I uninstalled and reinstalled Avast 5 the other day on the system I was talking about with this issue just to see if my installation was borked and it's doing the same thing. On reboots the exclamation point goes away faster, about a second, on cold boots i'll get the red x quickly and the exclamation point will hang there for about three seconds. We'll see if an update changes anything, until then i'm not going to mess with it again. But, Waking could be correct, what he says makes sense and is what I was thinking.
By the way the system with this issue has practically nothing loading on start besides the standard MS services. I have Sygate 5.6 starting with Avast, that's it. XP SP3, e6420 overclocked to 2.66 Ghz, 2 gigs of ram. The slower system(laptop) without this issue also has nothing loading besides the standard MS services and Sygate 5.6. AMD Turion 2 Ghz single core processor(not a X2), 1 gig of ram. It's running Media Center 2005 SP3. Same exact guts as XP but with the Media Center crap which I never use. The fast system blazes to the desktop( I told ya I run it lean) which is why I might be seeing the exclamation point, the laptop sits at the "welcome" screen for a bit which is maybe why when I get to the desktop on the laptop I don't see the same thing going on.