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Basically, to answer your question, no, there's no way to add a PCIe slot to your system that I know of. It's essentially because it has to do with the motherboard chipset (the southbridge, I believe, to be exact), and it creates lanes. These lanes are then distributed to the slots. 16 lanes are distributed to a PCIe lane, making it 16x. I'm trying to simplify it down slightly, as it's much more complicated than that.
Now, about your video card/system. What do you use your system for? You may want to look for a 7800GS, which I think is the latest/fastest AGP card out now. Also you could grab an extra gig of RAM for your system to bump it up to 2 gigs.
Unless your trying to run the latest games at max settings, I'd suggest you look at some of the upcoming processors and such, and think about holding off for a while to upgrade. There are a lot of impressive components coming out shortly (Core 2 Duo, for example, if it lives up to it's pre-release benchmarks). If I were you I'd think about saving up my money for a year and then buying the latest and greatest, but again, it's up to you so more memory and the 7800GS could be a good option for you.
Let us know how you make out! :)
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