When you say it's a PCI-to-USB-2 card, do you mean it transfers at USB 2.0 speeds? Assuming so...
Your USB 3.0 external drive will only run at USB 2.0 speeds when you connect it to a 2.0 connection on that XP machine, BUT... That still should be fast enough. USB 2.0 tops out at 480Mbps TECHNICALLY. But really you typically get half that. But since lossless standard definition video is usually in the 35Mbps range, and DV is 25Mbps, it should work. Just make sure you aren't doing any other significant movement of data across USB on that machine while capturing.
Now if that PCI card is old and only does USB 1.1 speed (12Mbps), the answer is a big fat NO. Or, if something else is going on with your machine such that it's not using that card correctly, or some other software/hardware issue is slowing it down, it may not work either.
Basically, try it! If you get dropped frames, it ain't fast enough. ;-)
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