Queues – yep I was talking about MSMQ Queues. You might be able to have a trigger in SQL collect the data and then send it to a MSMQ that biztalk will monitor. We did something like that with an integration project into Great Plains.
As far as web services go, in Biztalk 2004 if you want to call them without an Orchestration you need to use the WSE Adapter. Other then that, I have not worked with web service calls too much so you best bet would be to test it out.