It should be a given that people change their email address occasionally, and so using an email address as a unique user identifier is a bad idea - but nevertheless I've seen programmers do this on occasion, and I was reminded of this today when I contacted Tradeshift (an otherwise good invoicing startup) about why I couldn't change my email, and got the reply that email addresses were being used as user IDs, but "we're working on a different solution so that in time it'll be possible to change your email address." Hmm...
(Note: There's nothing wrong with using email addresses for log-ins, i.e. letting users enter their email address and password when they log in. But there should always be some sort of other unique user identifier (typically an integer) so that users may change their email address without breaking any database references).