Well, I haven't tried it myself, but in theory I think it should be possible.
Glancing at the ar_mailer documentation (http://seattlerb.rubyforge.org/ar_mailer/), the ActionMailer::ARSendmail class exposes a public instance method named deliver which accepts a collection of email objects as it's only argument and then sends those emails using the SMTP settings you've set in your environment file. Basically, when you run the ar_sendmail command (either from cron or the command line or whatever) it I'm pretty sure it eventually calls the deliver method to do its dirty work.
So, you could have a callback (i.e. after_create) that would call the deliver method manually only on the emails you want to send immediately. Make sense? Be sure to send a collection of emails (even if the collection is only one email long) to the method, because that's what it expects -- it uses methods like Array#shift which will throw an error if called on something other than some sort of collection.
Anyway, I haven't actually tried this, I'm just theorizing here, so your mileage may vary. Let me know what you figure out, and if I get some free time I may dig a bit deeper and test what I've just suggested to you. Also, check out the documentation to see if it's of any help.