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WinXP has some odd behavier. If it tries to access a normal file share it will also try to use WebDAV. These are the port 80 and 443 connections you are seeing. Hook up a sniffer to make sure. You will notice WinXP doing an OPTIONS /filename when it tries to access a share. This seems to be by design. Go figure.
Edit: This seems to be caused by the WebClient Service on XP. Try and disable this service and recheck. The WebClient service will try to use WebDAV to access the file/share before it will use smb.
Can you give me any more information on WEbDav, and this WEbclient Service, if so that WOULD BE GREAT. I think you have hit the nail on the head, and I am so releaved, but not 100 percent confident YET.