You have no way to find out who is trying to use the reset "Joe's" password. It could be Joe, or maybe someone poses as Joe.
An alternative to sending email is either calling one of Joe's phones using the one-time reset key, or sending an SMS message.
Calling Joe's phone with an audio message is easy from http://www.twilio.com/ But everyone can get a phone for Joe's office. Thus, you usually want to get an extra opportunity before calling. For example, a secret question / answer. Using the phone and the secret q & a, you made things tougher for the bad guys, but still doable by Joe.
Another idea is to send a reset message to someone who Joe trusts and who knows Joe. (Send by email or by phone / sms.) An option for this is to send to an employee who knows Joe, for example, his designated salesrep, HR rep, etc.
Use the message: send an email with street mail with the reset code. It will take a couple of days to get there, but mail theft is federal rap. See http://www.postalmethods.com/ If there are very bad negative results possible, this may be a good solution.
For any of the above, Joe will enter information when he sets up an account.
Another example is to require Joe to call the help desk and let the person interrogate him.
The bottom line is that no technique is perfect. See the history of twitter breaks: http://www.technewsworld.com/story/67612.html?wlc=1247790901&wlc=1248238327
Last thought: don't forget about antiphishing. Often done, letting Joe choose the image that the site will show him when he does something important. The idea is that a phishing site will not be able to replicate the user interface, thereby raising Joe's suspicions that he may not have reached the desired site.
Larry k
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